Resinous polymer sheet materials having selective, surface decorative effects and methods of making the same

ABSTRACT

Resinous polymer sheet materials having selective, surface decorative effects comprising: 
     (1) a base layer or substrate, such as a fibrous backing sheet material and/or a blown or unblown resinous polymer composition having either an embossed or a relatively smooth surface; 
     (2) a pattern or design printed or otherwise deposited on and adhered to the base layer or substrate, certain portions of the printed pattern or design having certain colors, and other portions of the printed pattern or design having other colors; and 
     (3) a wear layer having an embossed or a relatively smooth surface and containing reactive polymerizable monomers and having certain surface portions provided with a certain texture or effect, such as a flat, dead or dull mat finish, and other surface portions provided with another texture or effect, such as a sleek, glossy or lustrous finish, the interior portions of the wear layer lying under the flat, dead or dull mat finish having a relatively high melt viscosity and containing relatively high concentrations of polymerized and/or cross-linked reactive polymerizable monomers, and the interior portions of the wear layer lying under the sleek, glossy or lustrous finish having either (a) a relatively low melt viscosity and containing substantially no significant or substantial concentrations of polymerized and/or cross-linked reactive polymerizable monomers, or (b) a relatively high melt viscosity and containing relatively high concentrations of polymerized and/or cross-linked reactive polymerizable monomers, 
     (i) the certain colors of the printed pattern or design, and (ii) the flat, dead or dull mat finish areas, and (iii) the interior portions of the wear layer having a relatively high melt viscosity and containing the relatively high concentrations of the polymerized and/or cross-linked reactive polymerizable monomers all being in substantially perfect registry, and 
     (i) the other colors of the printed pattern or design, and (ii) the sleek, glossy or lustrous finish areas, and (iii) the interior portions of the wear layer having a relatively low melt viscosity and containing relatively low or no concentrations of polymerized and/or cross-linked reactive polymerizable monomers also all being in substantially perfect registry.

This patent application is a continuation-in-part of copending patentapplications Ser. No. 879,171, filed Feb. 21, 1978 and Ser. No. 942,246,filed Sept. 14, 1978, both abandoned.

THE FIELD OF THE INVENTION

The present invention relates to decorative sheet materials, and moreparticularly to decorative resinous polymer sheet materials havingcontrolled, selective placement of surface decorative effects of use as:floor, wall and ceiling coverings; desk, table and counter tops; surfacelayers on leather, fabrics, wood, paper, paper products, glass, metals,plastics, etc.; upholstery, drapery, clothing and apparel materials;interiors for cars, trucks, trains, airplanes, and other vehicles orother means of transportation; covers for books, periodicals and otherpublications; boxes, cartons, containers, and other receptacles; maps,road markers and similar and like articles. Even more particularly, thepresent invention is concerned with resinous polymer decorative sheetmaterials having smooth, glossy or lustrous surfaces in some areas; orembossed, dead or dull mat surfaces in other areas; or embossed, glossyor lustrous surfaces in still other areas; or smooth, dead or dull matsurfaces in still further areas; all of such areas sharply contrastingwith each other aand in perfect registry with a pattern or designprinted on such decorative sheet materials.

THE GENERAL BACKGROUND OF THE INVENTION

Decorative sheet materials of a resinous polymer composition have beenmanufactured for many years and one of the commonest means of creatingor enhancing the decorative effects has been to provide selectedportions of the surface of such decorative sheet materials withdifferent types of contrasting finishes or effects, or surface gloss orluster differentials, for example, with smooth, glossy or lustroussurfaces; embossed, dead or dull mat surfaces; embossed, glossy orlustrous; and smoth, dead or dull mat surfaces, all sharply contrastingwith one another.

Many methods, including differential mechanical embossing, inlaying, orchemical etching, and other methods, have been devised to provide suchsharply contrasting surfaces but all of such prior art methods havealways left something to be desired. For example, differentialmechanical embossing combined with pattern or design printing has alwayscreated registration problems and related difficulties. Inlaying andchemical etching methods have normally been costly and process-timeconsuming.

PURPOSES AND OBJECTS OF THE INVENTION

It is therefore a principal purpose and object of the present inventionto provide resinous polymer compositions in sheet material form havingselective, surface decorative effects created by the controlledplacement of various different surface finishes, embossings, or surfacegloss differentials wherein smooth or embossed glossy or lustroussurface areas sharply contrast with each other and with smooth orembossed dead or dull mat finishes surfaces, using methods in whichregistration problems and difficulties are substantially completelyeliminated and which methods are neither costly nor process-timeconsuming.

BRIEF SUMMARY OF THE INVENTION THE PRODUCT ASPECTS

It has been found that such principal purposes and objects, and otherprincipal purposes and objects which will become clear from a furtherreading and understanding of this disclosure, may be accomplished byproviding resinous polymer sheet materials having selective, surfacedecorative effects comprising: (1) a base layer or substrate, such as afibrous backing sheet material and/or a blown or unblown resinous sheetpolymer composition having an embossed or a relatively smooth surface;(2) a pattern or design printed on and adhered to the base layer orsubstrate, certain portions of the printed pattern or design havingcertain colors, and other portions of the printed pattern or designhaving other colors; and (3) a wear layer containing reactivepolymerizable monomers and having certain surface areas provided with acertain texture or effect, such as a dead or dull mat finish, such as aglossy or lustrous finish, the interior portions of the wear layer lyingunder the dead or dull mat finish having a relatively high meltviscosity and containing concentrations of polymerized and/orcross-linked reactive polymerizable monomers, and the interior portionsof the wear layer lying under the glossy or lustrous finish having arelatively low melt viscosity and containing substantially nosignificant concentrations of polymerized and/or cross-linked reactivepolymerizable monomers, the certain colors of the printed pattern ordesign, the dead or dull mat finish areas, and the interior portions ofthe wear layer having a relatively high melt viscosity and containingthe polymerized and/or cross-linked reactive polymerizable monomers allbeing in substantially perfect registry, and the other colors of theprinted pattern or design the glossy or lustrous finish areas, and theinterior portions of the wear layer having a relatively low meltviscosity and containing no substantial concentrations of polymerizedand/or cross-linked polymerizable monomers also all being insubstantially perfect registry.

THE METHOD ASPECTS

It has been found that such resinous polymer sheet materials havingselective placement of decorative surface effects may be made, forexample, by the following simplified and abbreviated illustrative methodwhich comprises; laying down or otherwise forming a base layer orsubstrate, such as a fibrous backing sheet material and/or anon-foamable or potentially foamable resinous polymer composition orplastisol, and/or other sheet materials; printing or otherwisedepositing on such base layer or substrate a pattern or design in whichcertain predetermined portions or colors contain a polymerizationinitiator or catalyst having a certain concentration or activity and inwhich other predetermined portions or colors either contain apolymerization initiator or catalyst having a different concentration oractivity, or else contain no polymerization initiator or catalyst atall; applying to the printed pattern or design a resinous polymer wearlayer containing substantially uniformly therein a reactive,polymerizable monomeric material; mechanically embossing or otherwisecreating on substantially the entire surface of the wear layer a desiredtexture or finish, such as a flat, dead or dull mat finish, at asufficiently elevated temperature, as to activate or decompose thepolymerization initiator or catalyst to polymerize and/or crosslink thereactive, polymerizable monomeric materials takes place selectively inthe wear layer.

It has been found that such heating to a sufficiently elevatedtemperature for a sufficient period of time and the accompanyingpressure during the mechanical embossing procedure polymerizes and/orcross-links the reactive, polymerizable monomeric materials and alsoincreases the melt viscosity of the wear layer but only in those areaslying directly over the polymerization initiator or catalyst. As aresult, in such areas, the mechanically embossed, flat, dead or dull matfinish or texture is better capable of resisting the softening and themelting effects of the elevated temperatures during any subsequentfusion and/or blowing or foaming operations and therefore such areasremain substantially as they were originally mechanically formed in suchareas.

But, in those other areas where no polymerization and/or cross-linkingof the reactive, polymerizable monomeric materials took place in theresinous wear layer and wherein the melt viscosity thereof did notmaterially increase, the mechanically embossed flat, dead or dull matfinish or texture is not capable of resisting the softening and meltingeffects of the elevated temperatures during any subsequent fusion and/orblowing or foaming operations and therefore softens and meltssufficiently as to flow together and form a sleek, glossy or lustrousfinish which contrasts sharply with the adjacent flat, dead or dull matfinish of the polymerized and/or cross-linked areas of higher meltviscosities.

It is to be appreciated that the above simplified and abbreviatedillustrative method is merely one of several variations capable ofmaking the resinous polymer sheet materials of the present invention;that it is merely illustrative of the broader aspects of the presentinvention; and that some conventional and standard steps, such as, forexample, heating, gelling, cooling, drying, etc., have been omitted forpurposes of clarity and brevity.

BRIEF DESCRIPTION OF THE DRAWINGS

In the following specification and accompanying self-explanatorydrawings, there are described and illustrated preferred and typicalembodiments of the present invention but it is to be appreciated thatthe present invention is not to be construed as limited to suchpreferred and typical embodiments as are specifically disclosed andillustrated therein but to include other similar and equivalentembodiments, as are determined by the scope and the spirit of theappended claims.

Referring to the accompanying self-explanatory drawings,

FIG. 1 is a fragmentary, diagrammatic, elevational, cross-sectional viewof one embodiment of the present invention, showing the resinous polymercomposition in its initial form, prior to heating and blowing.

FIG. 2 is a fragmentary, diagrammatic, plan view of the resinous polymercomposition of FIG. 1, but shown in its final form, after heating andblowing;

FIG. 3 is a fragmentary, diagrammatic, elevational, cross-sectional viewof the embodiment of FIG. 1, also shown in its final form after heatingand blowing, the cross-section being taken on the line 3--3 of FIG. 2;

FIG. 4 is a fragmentary, diagrammatic, elevational, cross-sectional viewof another embodiment of the present invention, showing the structurethereof, prior to heating and fusion;

FIG. 4A is a fragmentary, diagrammatic, elevational, cross-sectionalview of the embodiment of FIG. 4, showing the structure after heatingand fusion;

FIG. 5 is a fragmentary, diagrammatic, elevational, cross-sectional viewof still another embodiment of the present invention, showing thestructure thereof, prior to heating and blowing;

FIG. 5A is a fragmentary, diagrammatic, elevational, cross-sectionalview of the embodiment of FIG. 5, showing the structure thereof, afterheating and blowing and the subsequent removal of release paper;

FIG. 6 is a fragmentary, diagrammatic, elevational, cross-sectional viewof a further embodiment of the present invention showing the structurethereof, prior to heating and fusion;

FIG. 6A is a fragmentary, diagrammatic, elevational, cross-sectionalview of the embodiment of FIG. 6, showing the structure thereof, afterheating and fusion;

FIG. 7 is a fragmentary, diagrammatic, elevational, cross-sectional viewof a still further embodiment of the present invention, showing thestructure thereof, subsequent to heating and blowing;

FIG. 8 is a fragmentary, diagrammatic, elevational, cross-sectional viewof still another embodiment of the present invention, showing thestructure thereof, subsequent to heating and fusion of the resins;

FIG. 9 is a fragmentary, diagrammatic, elevational, cross-sectional viewof still another embodiment of the present invention, showing thestructure of the product, either prior to heating and fusion of theresin, if a blowing or foaming agent was included in the resinouspolymer composition, or subsequent to the heating and fusion of theresin, if no blowing or foaming agent was included in the resinouspolymer composition.

FIG. 10 is a fragmentary, diagrammatic, elevational, cross-sectionalview of the embodiment of FIG. 9, subsequent to the heating and fusionof the resin, plus blowing or foaming, when a blowing or foaming agentwas included in the resinous polymer composition;

FIG. 11 is a fragmentary, diagrammatic, elevational, cross-sectionalview of the embodiment of FIG. 10, subsequent to the heating and fusionof the resin, plus blowing or foaming, if a blowing or foaming inhibitorwas included in certain portions or areas of the applied printing inkcomposition; and

FIG. 12 is a fragmentary, diagrammatic, elevational, cross-sectionalview of the still further embodiment of the present invention, whereinthe free radical polymerization initiator, catalyst, or organic peroxideis contained in a separate layer of the product.

These Figures have not been drawn precisely or accurately to scale. Someportions and some dimensions therein have been drawn to a slightlylarger scale, whereas certain other portions and dimensions therein havebeen drawn to a slightly smaller scale. This has been done merely tobring out more clearly some of the details of the smaller portions andto accentuate some of the more important features and aspects of thepresent invention, such as the thickness of the printing ink compositionlayer which has been drawn increased manyfold in in the Figures.

GENERAL DESCRIPTION OF THE INVENTION FIGS. 1-3

The present invention will be generally described and illustratedprimarily with reference to FIGS. 1-3 which are illustrative but notlimitative of the scope of the broader aspects of the inventive concept.In these Figures, there is illustrated a resinous polymer sheet material10 comprising a base layer or substrate 11 of a relatively flat sheetbacking material 12 and a potentially foamable polymer composition 13which, after mechanical embossing at an elevated temperature and underpressure and after subsequent blowing and foaming at an even moreelevated temperature, possesses a relatively high, blown or foamed,uninhibited cellular resinous polymer composition 14 and a relativelylow, relatively unblown or unfoamed, inhibited, relatively orsubstantially non-cellular resinous polymer composition 16. The term"substantially non-cellular" does not mean completely non-cellular butdoes indicate that the cells therein, if any, are very much smaller insize and very much fewer in number than the cells in the so-calledcellular portions 14. A printing ink composition 18, in the form of adesired pattern or design usually containing many different colors, isapplied to the surface of the potentially foamable resinous polymercomposition 13, prior to the mechanical embossing at the elevatedtemperature and pressure and the subsequent blowing and foaming at theeven more elevated temperature.

The pattern or design of the printing ink composition 18 possessescertain predetermined areas or colors 20 which, in this embodiment,contain a blowing modifier, such as an inhibitor, and a free-radicalpolymerization initiator or catalyst, such as an organic peroxide.However, other predetermined areas or colors 21 do not contain anyblowing modifier or any free-radical polymerization initiator or anycatalyst, for purposes to become clearer from a further reading and anunderstanding of this specification. A resinous polymer composition inthe form of a wear layer 22 is applied substantially uniformly over theprinting ink composition 18.

As noted especially in FIG. 3, the blowing modifier or inhibitorrestricts the blowing or foaming of the potentially foamable resinouspolymer composition 13 in the areas A which correspond to and are inperfect registry with the areas 20. At the same time, blowing or foamingand expansion of the potentially foamable resinous polymer composition13 is not restricted or deterred in the areas B which do not liedirectly over the areas 20 containing the blowing modifier or inhibitor.Thus far, all this is conventional and generally standard.

It is also to be noted that the free-radical polymerization initiator orcatalyst which is also present in areas 20 causes, for reasons whichwill be explained in greater detail hereinafter, the surface areas ofthe wear layer 22 lying directly over the areas 20 to have an embossedflat, dead or dull mat finish or texture, whereas the other areas B ofthe wear layer 22 not lying directly over the areas 20 and which do notcontain any of the free-radical polymerization initiator or catalysthave a sleek, glossy or lustrous finish. The two types of finishes arein sharp contrast to each other.

It is also to be realized that the areas 20 not only contain thefree-radical polymerization initiator or catalyst, but also contain theblow modifier or inhibitor, as well as a predetermined pigment or colorof the printing ink composition 18, in accordance with the multicolorpattern or design. As a result, the embossed, flat, dead or dull finishor texture in areas A are in complete and perfect registry with therelatively low, unblown or unfoamed portions 16 of the resinous polymercomposition 13, as well as the predetermined pigment or color of thepattern or design. And, at the same time, the smooth, glossy or lustrousfinish in areas B are in complete and perfect registry with therelatively high, blown or foamed portions 14 of the resinous polymercomposition 13, as well as the other predetermined pigments or colors ofthe pattern or design.

More specific details of such constructions and their properties ofperfect registration of embossing, and finishes or textures, and blownor foamed areas, and their respective colorations, as well as themethods and procedures for obtaining such constructions will bedescribed in greater detail hereinafter with reference to the followingpreferred and typical embodiments of the present invention.

DESCRIPTION OF PREFERRED AND TYPICAL EMBODIMENTS OF THE INVENTION THEBASE LAYER OR SUBSTRATE

The base layer or substrate 11 may comprise a relatively flat, fibrousbacking sheet material 12 and/or a blown or unblown resinous polymercomposition having a chemically embossed or unembossed surface and/orother relatively flat sheet material.

THE BACKING SHEET MATERIAL

A relatively flat, backing web or sheet material 12 may be used, ifdesired or required, as the base layer or substrate 11 for the resinouspolymer sheet materials 10 of the present inventive concept. Such abacking sheet material 12 may comprise a felted or matted fibrous sheetof overlapping, intermingled fibers and/or filaments; or a non-woven,knitted, woven, or otherwise textile fabricated construction; or a sheetof resinous polymer composition; or paper or a paper product or similaror like equivalent constructions and materials. A felted fibrous sheetmaterial comprising inorganic fibers, such as asbestos; or organicfibers, such as cellulose, cotton, jute, or rayon; or synthetic orman-made fibers and/or filaments, such as polyolefins, polyamides,acrylics, glass, etc., is the most commonly employed backing sheetmaterial but many others are equally suitable and are utilizable inspecial situations. Such backing sheet materials are set forth in manyprior art patents, such as U.S. Pat. Nos. 3,293,094, 3,293,108, and3,660,186.

The thickness of such a relatively flat backing sheet material 12 willdepend to a large extent upon the particular product to be made and theparticular subsequent use for which it is intended. Normally, suchthicknesses are in the range of from about 10 mils to about 90 mils, butother thicknesses, expecially those greater than 90 mils, may be used inspecial and particular circumstances.

THE POTENTIALLY FOAMABLE OR NONFOAMABLE RESINOUS POLYMER COMPOSITION

The relatively flat backing sheet material 12 may be used by itself asthe base layer or substrate, or it may be used in conjunction with othersheet materials, such as, for example, a layer of potentially foamableor nonfoamable resinous polymer composition. Or the relatively flat,backing sheet material 12 may be omitted completely and the foamable ornonfoamable resinous polymer composition may be used by itself. Suchresinous polymer compositions may be made by well-known standard andconventional methods and may contain one or more synthetic resins, suchas a polymer or copolymer of vinyl chloride, or other resins, such aspolyurethanes, as the main constituent resin.

Other constituents of such resinous polymer compositions include: ablowing of foaming agent, such as azonicarbonamide, if a blowing orfoaming agent is desired; various accelerator/stabilizers or catalystssuch as dibasic lead phthalate, zinc octoate, zinc oxide, lead octoate,dibasic lead phosphite, etc.; various light and/or heat stabilizers, andmetallic soaps; plasticizers as dioctyl phthalate, butyl benzylphthalate, dibutyl sebacate, etc.; coloring agents and pigments astitanium dioxide; solvents and diluents as methyl ethyl ketone, mineralspirits etc.; fillers as clay and limestone; and many other conventionaland well-known additives and improvement agents.

Although a polymer or copolymer of vinyl chloride in the form of aplastisol is the preferred and typical synthetic resin to beincorporated into the resinous polymer composition, many other resinsare as equally applicable, not only in plastisol form but also inorganosol, latex, or solvent form. The specific resin and its particularform of use as they are utilized herein, do not relate to the essence ofthe inventive concept and many other suitable resins are set forth inthe United States Patents previously mentioned hereinbefore.

THE BLOWING OR FOAMING AGENT

Also, although azonicarbonamide is indicated herein and particularly inthe Examples as the preferred and typical blowing or foaming agent to beincluded in the resinous polymer plastisol composition, when blowing orfoaming is desired or required, many other similar or like equivalentblowing or foaming agents are also applicable within the principle ofthe present invention. The specific blowing or foaming agent which isused does not relate to the essence of the present invention and manyother suitable and acceptable blowing or foaming agents are to be notedin the previously mentioned United States Patents. All that is requiredis that the blowing or foaming agent has a sufficiently highdecomposition temperature that it is not activated or decomposedprematurely during the earlier procedures of heating, gelling, and themechanical embossing to be described hereinafter.

Specific blowing or foaming agents and their decomposition temperaturesat which they release gas vigorously include: azodicarbonamide (390° F.)N, N'-dimethyl-N, N'-dinitrosoterephthalamide (220° F.);azobisisobutyronitrile (240° F.); p,p'-oxybis (benzenesulfonylhydrazide)(320° F.) dinitrosopentamethylenetetramine (80%) (370° F.); p,p'-oxybis(benzenesulfonylsemicarbazide) (425° F.); barium azodicarboxylate (above480° F.) and many others. Such decomposition temperature values relateto the release of gas vigorously in dioctyl phthalate.

OTHER CONSTITUENTS OF THE RESINOUS POLYMER COMPOSITION

In a similar way, many other accelerators, initiators, catalysts,viscosity improvers, light and heat stabilizers, uv absorbers, dyes,pigments, plasticizers, antioxidants, fillers, bacteriostats andbacteriocides, and many other additives may be included in the resinouspolymer composition. The specific nature and the particular physical andchemical properties and characteristics of the various constituents ofthe resinous polymer composition do not relate to the essence of thepresent inventive concept and further specific elaboration of suchadditives is believed unnecessary and not required. All of theseconstituents are well known and conventional in the industry and manyare set forth in the previously mentioned United States Patents.

The resinous polymer composition is also preferably a dispersion of asynthetic resin in a liquid medium. The dispersion medium can be aplasticizer in the case of a plastisol, or water in the case of anaqueous latex, or it can be an organic solvent in the case of anorganosol. Excellent results are obtained with a dispersion of asynthetic resin in a plasticizer as a plastisol and such form is thepreferred and typical form for the application of the present invention.

A few preferred and typical plasticizers useful in forming suchplastisols are dibutyl sebacate, dioctyl sebacate, dioctyl adipate,didecyladipate, dioctyl azelate, dibutyl phthalate, dicapryl phthalate,dioctyl phthalate, dibutoxy ethyl phthalate, tricresyl phosphate, octyldephenyl phosphate, dipropylene glycol dibenzoate, butyl benzylsebacate, dibenzyl sebacate, dibenzyl phthalate, butyl benzyl phthalate.

It is to be appreciated that, although plastisols will be used tofurther describe the present invention, such is not intended to excludethe use of organosols or aqueous latices which are also utilizable.

THE POTENTIALLY FOAMABLE PLASTISOL COMPOSITION

A few preferred and typical potentially foamable plastisol compositionsare as follows:

    __________________________________________________________________________    (Parts by weight, based on 100 parts of resin, phr)                           __________________________________________________________________________                   P-6                                                                              P-7 P-8 P-5 P-9                                                                              P-2                                          __________________________________________________________________________    Polyvinyl chloride, dispersion                                                grade, inh. viscosity 1.0                                                                    50     100     25 75 a                                         Polyvinyl chloride, dispersion                                                grade, inh. viscosity 0.9                                                                    50 100     100 50    b                                         Polyvinyl chloride, blending                                                  resin, inh. viscosity 0.9     25 25 c                                         Alkyl benzyl phthalate              d                                         Polydodecyl benzene              12 e                                         Alkyl aryl modified phthalate                                                 ester          55                   f                                         Alkyl aryl hydrocarbon                                                                       10     5             g                                         Di(2-ethyl hexyl phthalate                                                                          60  57     7.09                                                                             h                                         Butyl benzyl phthalate                                                                          57          57 38 i                                         Epoxidized esterified tallate       j                                         Mineral spirits (boiling point                                                range 300° F.-425° F. k                                         Diphenyl decyl phosphite            l                                         Dibasic lead phosphite                                                                       1.5                                                                              1.11                                                                              1.0 1.11                                                                              1.11                                                                             1.11                                                                             m                                         Zinc oxide                          n                                         Zinc octoate (18% Zn)               o                                         Lead octoate (24% Pb)               p                                         Titanium dioxide                                                                             5  5.29                                                                              2   5.29                                                                              5.29                                                                             5.29                                                                             q                                         Azodicarbonamide                                                                             2.5                                                                              2.53                                                                              3   2.53                                                                              2.53                                                                             2.53                                                                             r                                         Anhydrous alumina silicate          s                                         __________________________________________________________________________    P-10                                                                             P-11                                                                              P-12                                                                             P-13                                                                             P-14                                                                             P-1 P-3 P-15 P-4 P-16                                         __________________________________________________________________________              50 50 70                  a                                         75 100 75 50 50     75  100  75  75 b                                         25     25       30  25       25  25 c                                                         16.8                d                                                12 12 12 13.3                                                                              12       12  13.5                                                                             e                                                                             f                                                                             g                                                8.02                                                                             4.2                                                                              3.27                                                                             2.91                                                                              2.52                                                                              62.5 2.53                                                                              6.36                                                                             h                                         58 53  38 38 38 27.7                                                                              38       38  31.5                                                                             i                                            5      5                      5.1                                                                              j                                         1.55                                                                             1.55                                                                              1.55                                                                             1.55                                                                             1.55   1.55                                                                              1.55 1.55                                                                              1.55                                                                             k                                                                             l                                            3      1.0                       m                                            0.83         0.86                n                                                      1.0    0.95                                                                              0.95        o                                         1.2    1.11                  1.0 1.0                                                                              p                                         5.29                                                                             5.29                                                                              5.29                                                                             5.29                                                                             5.29                                                                             3.64                                                                              5.29                                                                              5.29 5.29                                                                              5.29                                                                             q                                         2.53                                                                             2.53                                                                              2.53                                                                             2.5                                                                              2.53                                                                             2.32                                                                              2.53                                                                              2.53 2.53                                                                              2.53                                                                             r                                                         12.3                s                                         __________________________________________________________________________

The letters which have been positioned at the right hand side of eachportion of the preceding table are used merely to facilitate the readingand the understanding of each portion of the table. They have no othersignificance.

All the plastisol compositions set forth in the preceding table arefoamable resinous polymer compositions, inasmuch as azodicarbonamide isincluded in all the formulations. Such a blowing agent would be excludedif a non-foamable resinous polymer composition was desired or required.

If no backing sheet material such as a felted or matted fibrous web isto be used, then the plastisol may be doctored by a doctor blade, orroll coated, or poured, or cast, or otherwise applied to a strippablecarrier which may be a steel belt, a rubber belt, release paper, or afelt or other fabric or material having a release coating thereon andsubsequently stripped therefrom.

However, if a backing sheet material is to be used and is to remain as apart of the final product, then the plastisol may be doctored by adoctor blade, or roll coated, or poured, or cast, or otherwise appliedand adhered to the carrying sheet material in a substantially uniformmanner in a relatively uniform thin coating by procedures well-known inthe art. The thickness of such a plastisol coating as a foamableresinous polymer composition, as applied and still wet, is in the rangeof from about 5 mils to about 50 mils, or even more, if so desired orrequired. After the plastisol has been applied to the carrying backingsheet material, it is then heated under relatively gentle or moderateheat in an oven or other suitable heating device for a period of time offrom about 1 minute to about 4 minutes at an elevated temperature offrom about 240° F., to about 470° F., but more normal commercially fromabout 290° F., to about 350° F., whereby the plastisol firms and gels sothat it can be more easily handled and processed subsequently. Thetemperature and time relationships are mutually interdependent and thehigher the temperature, the shorter is the required time, and viceversa. The elevated temperature, however, is not sufficiently high as toactivate or to decompose the particular blowing or foaming agent whichmay be present as to cause blowing or foaming of the resinous polymercomposition.

THE PRINTING OF THE GELLED RESINOUS POLYMER COMPOSITION

The gelled, firm resinous polymer composition is then cooled and isprinted or coated with a suitable printing ink composition in thedesired or required pattern or design which may possess many colors. Theparticular pattern or design which is used does not relate to theessence of the invention and any suitable pattern or design may beselected.

The printing procedure is conventional and should require no furtherdescription, inasmuch as such procedures are well known in the industryand are described in many prior art patents. If it is desired thatdifferent levels of heights of the blowing or foaming effects beobtained, then, predetermined parts or portions of the pattern or designprinted on the surface of the resinous polymer composition contain ablow modifier or inhibitor in different amounts, concentrations, ortypes, and so forth, depending upon the variety of differential blowingor foaming effects desired. Such differential effects are well describedin the previously mentioned United States Patents and should need nofurther explanation or description.

Naturally, if no differential effects are desired as a result of theblowing or foaming procedure, then, no blow modifying agents orinhibitors are included in the printing ink composition and the levelsand the extent of the blowing or foaming action is generally uniform.Some typical and well known conventional printing ink compositions arenoted in the previously mentioned United States Patents.

THE FREE-RADICAL POLYMERIZATION INITIATOR OR CATALYST

Additionally, there is included in certain predetermined parts orportions of the selected printed pattern or design a polymerizationinitiator or catalyst for a purpose to be described hereinafter morefully, with reference to certain reactive polymerizable monomers also tobe described more fully hereinafter.

The concentration of the free-radical polymerization initiator orcatalyst in the printing ink composition will vary and will range fromabout 1 percent by weight to about 35 or 40 percent by weight, andpreferably from about 1 percent to about 10 percent by weight, based onthe total weight of the printing ink composition.

These free-radical polymerization initiators or catalysts, as they areoften referred to in the industry, are perhaps more properly identifiedas organic peroxides, or per-compounds, which materials are largelychemically characterized by the presence in their structure of thethermally unstable oxygen-oxygen grouping (that is, --O--O--, a peroxygroup). Such a group decomposes, normally upon being heated to certainelevated temperatures, to form free radicals to initiate thepolymerization reaction. The specific free-radical polymerizationinitiator or catalyst which is selected for a particular polymerizationor reaction depends upon the temperature at which the specific reactionor polymerization takes place, upon the rate of decomposition of thefree-radical polymerization initiator or organic peroxide, upon the rateof generation or free radicals, upon the presence of metal ions or bythe solvents of diluents in which the organic peroxides are oftensupplied commercially, upon the percent peroxide and the percent oxygenin the assay, upon the activation energy (k cal per mole), etc.

From a further reading and understanding of this disclosure, it willbecome apparent that dicumyl peroxide is the preferred and typicalorganic peroxide or free-radical polymerization initiator or catalyst,of use with the majority of polymerizable reactive monomers. Suchpreference is due basically to the fact that dicumyl peroxide fits invery desirably with respect to its one minute half-life temperature inrelationship to the normal gelling temperature of the plastisol used, tothe normal fusion temperature of the resinous polymer composition used,and to the normal decomposition temperature of the blowing or foamingagent used (azodicarbonamide). However, it is to be understood that manyother organic peroxides or free-radical polymerization initiators orcatalysts are suitable and satisfactory for applying the principles ofthe present inventive concept. For example, di-butyl tin dilaurate wouldbe a preferred and typical cross-linking catalyst, if a differentresinous polymer composition, such as a polyurethane, is used. Otherpreferred and typical organic peroxides and per-compounds include:

Di-t-butyl peroxide

2,5-dimethyl-2,5-bis(t-butylperoxy) hexane

2,5-dimethyl-2,5-bis(t-butylperoxy) hexyne-3

di-t-amyl peroxide

t-butyl-2-hydroxyethyl peroxide

a,a'-bis(t-butylperoxy) diisopropyl benzene

benzoyl peroxide

diisobutyryl peroxide

2,4-dichlorobenzoyl peroxide

diisononanoyl peroxide

decanoyl peroxide

lauroyl peroxide

acetyl peroxide

succinic acid peroxide

bis-p-chlorobenzoyl peroxide

2,5-dihydroperoxy-2,5-dimethyl hexane

cumene hydroperoxide

t-butyl hydroperoxide

p-menthane hydroperoxide

diisopropylbenzene hydroperoxide

1,1,3,3-tetramethyl butyl hydroperoxide

di(n-propyl)peroxy dicarbonate

diisopropyl peroxydicarbonate

di(sec-butyl) peroxydicarbonate

di(2-ethylhexyl) peroxydicarbonate

dicyclohexyl peroxydicarbonate

dicetyl peroxydicarbonate

bis(4-t-butylcyclohexyl) peroxydicarbonate

t-butylperoxy isopropyl monocarbonate

2,2'-azobis(isobutyronitrile)

1,1-bis(t-butylperoxy)-3,3,5-trimethyl cyclohexane

t-butyl peroxyacetate

t-butyl peroxyisobutyrate

t-butyl peroxy-2-ethylhexanoate

t-butyl peroxypivalate

t-butyl peroxyneodecanoate

t-butyl peroxymaleic acid

di-t-butyl diperoxyphthalate

2,5-dimethyl-2,5-bis(benzoylperoxy) hexane

2,3-dimethyl-2,5-bis(octanoylperoxy) hexane

t-butyl peroctoate

t-butyl perbenzoate

acetyl cyclohexyl sulfonyl peroxide

acetyl sec-heptyl sulfonyl peroxide

2-t-butylazo-2-cyano-4-methoxy-4-methyl pentane

2-t-butylazo-2-cyano-4-methyl pentane

2-t-butylazo-2-cyanopropane

methyl ethyl ketone peroxide

2,4-pentanedione peroxide

cyclohexanone peroxide

It is to be noted that compounds cover several classes of peroxides andencompass a very wide range, all of which, nevertheless, are utilizableunder selected conditions, with particular reference to the plastisolgelling temperature, the plastisol and resinous polymer compositionfusion temperatures, and the blowing and foaming temperatures, which,with respect to the preferred operating conditions of the presentinventive concept, are normally commercially in the range of about 300°F., 350° F., and 395° F., respectively. For the specific purposes of thepresent invention, a preferred range of peroxides is noted as possessingone minute half-lives of from about 272° F. to about 376° F., withespecially preferred commercial ranges of one minute half-lives of fromabout 305° to about 345° F.

The preferred ranges of the one minute half-lives of from about 272° F.to about 376° F., as will be discussed in greater detail hereinafterwill most easily permit satisfactory and sufficient cross-linking of thereactive polymerizable monomer in the upper wear layer to occur afterthe plastisol gelling operation and primarily during the mechanicalembossing operation, or perhaps even during the early part of theblowing and foaming operation. In this way, the mechanical embossmenttakes place after the gelling operation and is then retained throughoutthe blowing and foaming cycle in those areas where cross-linking of thepolymerizable reactive monomer has taken place. If cross-linking of thereactive polymerizable monomer were to take place too early in theover-all procedure, such as before or during the initial plastisolgelling operation, then the desired mechanical embossment may becomedifficult or even impossible to obtain. In the same way, ifcross-linking of the polymerizable reactive monomer were to take placetoo late, such as during the latter part of the blowing or foamingoperation, then, perhaps, it may be too late for certain embossed areasof the wear layer to retain their mechanical embossment.

The concentration of the remaining constituents of the printing inkcompositions which includes resins, pigments and dyes, solvents anddiluents, blow modifiers and inhibitors, plasticizers, etc., areconventional and are within the ranges noted in the prior art, such asthe previously mentioned United States Patents. With particularreference to the blow modifiers or inhibitors, it is to be stated that,although essentially all of the blow modifiers or inhibitors mentionedin these United States Patents are utilizable within the broader aspectsof the present invention, three preferred and typical examples of suchare trimellitic anhydride, fumaric acid, and benzotriazole.

A few preferred and typical printing ink compositions are as follows:

    __________________________________________________________________________    (Parts by weight) (or percent, if total of parts equals                       __________________________________________________________________________    100)                                                                                              P-0  P-00 P-1  P-2  P-3  P-4                              __________________________________________________________________________    a   Vinyl chloride-vinyl acetate                                                  copolymer 90/10 6.6  6.8  9.5  10.1 9.7  10.4                             b   Methyl ethyl ketone                                                                           37.4 38.2 53.5 57.4 54.7 58.6                             c   Titanium dioxide                                                              ink concentration, 55%                                                                        25   25             2.8  3.0                              d   Carbon black vinyl ink    7.0  7.5  2.8  3.0                              e   Trimellitic anhydride                                                                         30   20   25   25   25   25                               f   Fumaric acid 62.5% in                                                         dioctyl phthalate                                                         g   Benzotriazole                                                             h   Dicumyl peroxide                                                                              1.0  10   5.0       5.0                                   i   t-butyl peroxybenzoate                                                    j   t-butyl peroxyoctoate                                                     k   di-t-butyl peroxyphthalate                                                l   2,5-dimethyl-2,5-di(t-                                                        butyl-peroxy) hexane                                                      m   1,1-bis(t-butyl peroxy)-3,3,5-                                                trimethyl cyclohexane                                                     n   t-butyl peroxy isopropyl                                                      carbonate                                                                 o   di-t-butyl peroxide                                                       p   Benzoyl peroxide                                                          q   t-butyl hydroperoxide                                                     __________________________________________________________________________      P-5                                                                              P-6                                                                              P-7                                                                              P-8                                                                              P-9                                                                              P-10                                                                             P-11                                                                             P-12                                                                             P-13                                                                             P-14                                                                             P-15                                                                             P-16                                                                             P-17                                                                             P-18                                                                             P-19                                                                             P-20                           __________________________________________________________________________    a 12.5                                                                             12.5                                                                             7.1                                                                              9.5                                                                              8.8                                                                              6.8                                                                              10  10                                                                              8.2                                                                              10.3                                                                             10.5                                                                             9.9                                                                              10 9.5                                                                              9.5                                                                              9.5                            b 70.5                                                                             70.5                                                                             40.1                                                                             53.5                                                                             49.7                                                                             38.2                                                                             56.6                                                                             56.6                                                                             46.7                                                                             58.1                                                                             59.7                                                                             55.8                                                                             56.6                                                                             53.5                                                                             53.5                                                                             53.5                           d 7.0                                                                              7.0                                                                              5.3                                                                              7.0                                                                              6.5                                                                              5.0                                                                              7.4                                                                              7.4                                                                              6.1                                                                              7.6                                                                              7.8                                                                              7.3                                                                              7.4                                                                              7.0                                                                              7.0                                                                              7.0                            e             25       20                25 25 25                             f       40       40       32                                                  g          20       18       19 16 20 18                                      h 10    7.5                                                                              10                                                                 i                               6.0                                           j                                  7.0                                        k             10 10 8.0                                                       l                                        5.0                                  m                                     8.0                                     n                      6.0                                                                              7.0                                                                              5.0                                              o                                           5.0                               p    10                                                                       q                                              5.0                            __________________________________________________________________________

THE WEAR LAYER

The printed, gelled potentially foamable plastisol is then allowed todry and a wear layer in the form of a resinous polymer composition orplastisol is then applied thereto. Such a wear layer compositioncontains conventional or standard constituents, such as resins(preferred and typical being polyvinyl chloride, medium to low molecularweight), plasticizers, stabilizers, pigments or dyes (on rare occasion),solvent and diluents, viscosity improvement and controlling agents, andlike additives and materials. The concentrations of such constituentsare conventional and standard and are in the ranges set forth in thepreviously cited United States Patents.

Additionally, however, there is also included in the wear layercomposition a further ingredient comprising one or more reactivepolymerizable monomeric materials, the polymerization and/orcross-linking of which can be initiated by the previously describedpolymerization initiators or organic peroxides. Such polymerizationinitiators are advantageously located in certain predetermined portionsor colors of the pattern or design of the printing ink composition,whereby certain predetermined portions of the reactive polymerizablemonomers lying directly thereover are polymerized and/or cross-linked,whereas certain other predetermined portions or colors of the pattern ordesign of the printing ink composition which do not contain anypolymerization initiator therein do not polymerize and/or cross-link thereactive polymerizable monomers lying thereover.

The inherent viscosities of the polyvinyl chloride resins used in suchwear layer compositions are in the range of from about 0.6 to about 1.2but, depending upon conditions and circumstances, may be as high asabout 1.6, as measured and determined by A.S.T.M. D-1243-66 prior to theinitiation of the mechanical embossing procedure, which will be morefully described hereinafter.

THE REACTIVE POLYMERIZABLE MONOMERS

The reactive polymerizable monomers are included substantially uniformlyin the wear layer and are polyfunctional and contain at least twoolefinically unsaturated sites in its molecule. Such monomers must becapable of polymerization at desired elevated temperatures usuallyhigher than the plastisol gelling temperature but lower than the blowingagent decomposition temperature. Such polymerization takes place in allareas of the wear layer which are lying directly over the free-radicalpolymerization initiator or organic peroxide located in certain selectedportions or colors of the printing ink composition.

Preferred and typical reactive polymerizable monomers include:

Diallyl fumarate

Diallyl maleate

Diallyl itaconate

Diallyl Phthalate

Ethylene glycol dimethacrylate

Ethylene glycol diacrylate

Diethylene glycol dimethacrylate

Diethylene glycol diacrylate

Triethylene glycol dimethacrylate

Triethylene glycol diacrylate

Tetraethylene glycol dimethacrylate

Tetraethylene glycol diacrylate

Polyethylene glycol dimethacrylate

Polyethylene glycol diacrylate

1.3-butylene glycol dimethacrylate

1.4-butylene glycol dimethacrylate

1,3-butylene glycol diacrylate

1,4-butylene glycol diacrylate

1,4-butanediol diacrylate

1,6-hexanediol dimethacrylate

1,6-hexanediol diacrylate

Allyl methacrylate

Allyl acrylate

Neopentyl glycol diacrylate

Neopentyl glycol dimethacrylate

Bisphenol A dimethacrylate (ethoxylated)

Divinyl benzene

Divinyl toluene

Trimethylolpropane trimethacrylate

Trimethylolpropane triacrylate

Pentaerythritol triacrylate

Glyceryl trimethacrylate

Triallyl cyanurate

Pentaerythritol tetraacrylate

Pentaerythritol tetramethacrylate

1,4-Butanediol Dimethacrylate

It is to be noted that such monomers are polyfunctional and includedifunctional, trifunctional and tetrafunctional monomers. However, ifdesired, a certain amount of monofunctional monomers may be included inthe wear layer in admixture with the polyfunctional monomers. Suchcombinations often possess unique and very desirable characteristics andproperties.

When monofunctional monomers are included with the polyfunctionalmonomers, they are present in amounts of from about 5% by weight toabout 50% by weight, based on the total weight of all monomers in theresinous wear layer formulation. The total weight of all monomers in thewear layer is in the range of from about 5 parts by weight to about 40parts by weight, based on 100 parts by weight of resin (phr) in the wearlayer formulation, or preferably from about 15 parts by weight to about35 parts by weight, based on 100 parts of resin (phr) in the resinouswear layer formulation.

The particular reactive polymerizable monomer or monomers which areselected for a particular use must, of course, be compatible with ordispersible in the resin representing the major constituent in theresinous wear layer formulation. It is usually contained in a copolymer,polymer or homopolymer of polyvinyl chloride. That is, the reactivepolymerizable monomer must be miscible or dispersible in substantiallyall proportions with the main resin and must be capable of being easilyand intimately dissolved or dispersed therein without separating intoseparate, distinct layers or portions, or occupying separate, discreteportions or phases in the resinous wear layer composition. And, ofcourse, the reactive polymerizable monomer must also be relatively inertat low temperatures and non-reactive with respect to the otherconstituents of the resinous wear layer composition.

The thickness of such a resinous wear layer composition, as firstapplied to the printed pattern or design and still wet, is in the rangeof from about 2 mils to about 30 mils, or greater, if so required byspecial circumstances, requirements, or conditions.

Preferred and typical formulations for the wear layer are noted in thepreviously cited United States Patents, except that the reactivepolymerizable monomer or monomers are not included therein.

After the wear layer containing the reactive polymerizable monomers hasbeen applied and adhered to the printed pattern or design of theprinting ink composition, it is heated under moderately gentle heat inan oven or other suitable heating device for a period of time of fromabout 1 minute to about four minutes at an elevated temperature of fromabout 240 ° F. to about 470° F., whereby it hardens or firms and gels sothat it can be easily handled in further operations. The temperature andtime are so interrelated as to be interdependent and the higher thetemperature, the shorter is the time of application of the heat, andvice versa. The elevated temperature, however, must not be that high asto activate or decompose the blowing or foaming agent which is normallypresent. Also, the temperature and the time must not be that great as tobring about a polymerization of the reactive polymerizable monomers inthe wear layer.

As will become evident from a further reading and understanding of thisdisclosure, it is normally contemplated that the polymerization andcross-linking of the monomers in the wear layer take place during theembossing procedure which follows and which takes place under about thesame temperature as the preceding gelling procedure but under additionalpressure whereby the embossing of the surface of the wear layer and thepolymerization of the reactive polymerizable monomers take place in thesame operation.

As mentioned hereinbefore, such temperatures are, of course, below thetemperature at which the blowing or foaming agent in the plastisolcomposition will be activated or decompose to release their gases in avigorous manner.

A few preferred and typical wear layer compositions are as follows:

    __________________________________________________________________________    (Parts by weight, based on 100 parts of resin, phr)                           __________________________________________________________________________                            W-1    W-2    W-3                                     __________________________________________________________________________    Polyvinyl chloride, low molecular weight,                                     dispersion grade, inherent viscosity 0.8                                                              100    100    100    a                                Di(2-ethylhexyl) phthalate     5.0           b                                Tricresyl phosphate                          c                                Epoxidized soya oil     2.7    2.7    2.7    d                                Alkyl aryl modified phthalate ester          e                                Epoxidized tall oil ester                    f                                2,2,4-trimethyl-1,3-pentanediol diisobutyrate                                                         3.7    3.7    3.7    g                                Butyl benzyl phthalate  15.5   15.5   15.5   h                                Polydodecyl benzene     4.6    4.6    4.6    i                                Ba-Zn phosphite stabilizer                                                                            6.6    6.6    6.6    j                                Nonyl phenyl polyethylene glycol ether       k                                Ethyl-2-cyano-2,3-diphenyl acrylate          l                                Violet toner                                 m                                Pentaerythritol tetramethacrylate            n                                Glyceryl trimethacrylate                     o                                Pentaerythritol triacrylate                  p                                Neopentyl glycol diacrylate                  q                                Trimethylolpropane trimethacrylate                                                                    25                   r                                Polyethylene glycol dimethacrylate                                                                           20            s                                Tetraethylene glycol dimethacrylate   27     t                                Ethylene glycol dimethacrylate               u                                1,3-butylene glycol dimethacrylate           v                                1,6-hexanediol dimethacrylate                w                                Triethylene glycol dimethacrylate            x                                Ethoxylated bisphenol A dimethacrylate       y                                Diethylene glycol dimethacrylate             z                                __________________________________________________________________________    W-4 W-5 W-6 W-7 W-8 W-13                                                                              W-14                                                                              W-9 W-10                                                                              W-12                                                                              W-15                                                                              W-11                              __________________________________________________________________________    100 100 100 100 100 100 100 100 100 100 100 100 a                             2.0             4.0 8.0         5.0 1.0         b                                                                             c                             2.7 2.7 2.7 2.7 2.7 2.7 2.3 2.7 2.7 2.7 2.7 2.7 d                                                     21.1                    e                                                 2.7                         f                             3.7 3.7 3.7 3.7 3.7 8.0 3.2 3.7 3.7 3.7 3.7 3.7 g                             15.5                                                                              15.5                                                                              15.5                                                                              15.5                                                                              15.5                                                                              8.0     15.5                                                                              15.5                                                                              15.5                                                                              15.5                                                                              15.5                                                                              h                             4.6 4.6 4.6 4.6 4.6         4.6 4.6 4.6 4.6 4.6 i                             6.6 6.6 6.6 6.6 6.6 6.6 6.6 6.6 6.6 6.6 6.6 6.6 j                                                     1.3                     k                                                     0.38                    l                                                     0.01                    m                                                                     25      n                                                                 24          o                                                             20              p                                                         25                  q                                                 25                          r                                                     25                      s                                                                             t                             23                                              u                                 25                                          v                                     28                                      w                                         27                                  x                                             21                              y                                                                         28  z                             __________________________________________________________________________

THE MECHANICAL EMBOSSING PROCEDURE

In the following description of the mechanical embossing procedure.emphasis will be placed on the obtaining of a flat, dead or dull matfinish or texture which is roughened, corrugated, contoured, knurled,lined, or the like. Such may be obtained by means of proper pressuredies or similar tools, or by pressing the surface of the wear layeragainst a roughened or desirably corrugated or contoured surface, suchas a fibrous paper surface, an uneven or roughened metallic surface, afabric, or any coarse, grainy surface which is not smooth, sleek, glossyor lustrous.

The depth of the mechanical embossing may be as little as a fraction ofa mil or it may be as much as about 15 mils, but preferably is fromabout 1 mil to about 4 mils, depending upon the type, thickness, and thenature of the wear layer being so embossed mechanically, upon thedecorative effect which is desired or required, upon the type and theform of the mechanical embossing, and so forth.

At the conclusion of the mechanical embossing procedure, the entiresurface of the wear layer is embossed so as to give it temporarily thedesired flat, dead or dull mat finish or texture allover. Such a finishor texture is substantially completely lacking in brilliance, gloss,luster or sheen. The surface may be roughened, corrugated, coarse, linedor knurled in a regular or irregular, predetermined or random fashionand may possess numerous very small knobs, projections, ridges, points,or protuberances to give it the desired flat, dead or dull matappearance. The mechanical embossing may also take the form of verymany, very fine lines which are straight and parallel are swirlingcurves, as many as about 60 or 80 or even 100 or more lines per inch, orit may be the result of pressing paper, textured materials or fabrics,woven, knitted or nonwoven against the surface of the wear layer tocreate thereon the desired finish or texture.

The mechanical embossing to yield the desired flat, dead or dull matfinish or texture or other finishes may take place under pressures whichmay be as low as about 2 pounds per square inch gauge up to about 300pounds per square inch gauge, depending upon the existing temperaturewhich is in the range of from about 240° F., to about 470° F. If thepressure is applied in a press platen, the pressure may be maintainedfor a period of time of from about 10 seconds to as much as about 4minutes. If the pressure is applied by means of a heated embossing roll,then the temperatures and the pressures will be in the higher portionsof the aforementioned ranges, whereas the time of the application of thepressure will be correspondingly relatively short. However, the passingor the wrapping of the resinous polymer sheet material around a portionof the periphery of the heated embossing roll can be used to extend theduration of the application of heat. The pressures which are exerted,however, must be sufficient as to establish a good intimate contactbetween the heated embossing surface and the resinous polymericmaterials being embossed.

The temperatures and the pressures which are realized during theembossing procedure are normally sufficient to activate or decompose thefree-radical polymerization catalyst or organic peroxide in thepredetermined portions of the printing ink composition which will bringabout a polymerization or a cross-linking of the reactive polymerizablemonomers lying over such predetermined portions. As a result, suchportions of the wear layer possess an increased melt viscosity thereinand a harder, more resistant surface which is capable of resisting anysoftening or melting tendencies during the subsequent heating involvedin the blowing or foaming procedure. In this way, such portions arecapable of retaining their flat, dead or dull mat embossed surfacefinishes or textures through the higher heating during the blowing andfoaming operations.

On the other hand, however, those predetermined portions of the wearlayer which lie over those portions of the printing ink compositionwhich do not contain any free-radical polymerization initiator ororganic peroxide are not materially polymerized or cross-linked, do notpossess an increased melt viscosity and do not obtain a harder or moreresistant surface and, consequently, when they are exposed to thegreater heat of the blowing or foaming operation, they will not be ableto resist any softening or melting tendencies, which are created andthey will melt and soften and flow to fuse into a glossy, lustrousfinish having a relatively high brilliance and sheen. Such a glossy,lustrous surface is very smooth and very planar and very reflective ofany light incident thereon, as contrasted sharply to the flat, dead ordull mat finish which is not smooth or sleek and is not as reflective ofany light incident thereon. The contrast created by these two types offinishes or textures is striking.

The final resulting product, in one form thereof, greatly resembles aceramic tile flooring such as is commonly found in bathrooms, both asfloor and as wall surfaces. The sleek, glossy or lustrous finish greatlyresembles the surface of a glazed or fired ceramic tile, whereas theflat, dead or dull mat surface greatly resembles the grout orcementitious materials which are placed between the glazed ceramic tile.Such unusual and strongly contrasting finishes and textures are broughtabout during and as a result of the more elevated temperatures whichprevail during the blowing and foaming operation.

THE BLOWING OR FOAMING OPERATION

The multi-layered assembly comprising: the backing sheet material and/orthe potentially foamable (or non-foamable) plastisol; the printedpattern or design of the printing ink composition, portions or colors ofwhich contain modifiers or inhibitors and free-radical polymerizationinitiators or organic peroxides, other portions or colors of which donot contain modifiers or inhibitors or free-radical polymerizationinitiators or organic peroxides; and the upper wear layer containingsubstantially uniformly therein the reactive polymerizable monomers,after being mechanically embossed over its entire surface, is heated toa sufficiently elevated temperature which is capable of fusing theresins in the resinous polymer compositions and which is also capable ofactivating or decomposing the blowing or foaming agents in thepotentially foamable plastisols to cause vigorous blowing or foamingtherein. Further, the surface of the wear layer is raised to the morehighly elevated temperature whereby those areas thereof, which do notpossess the higher melt viscosities or the polymerized or cross-linkedmonomers, soften, melt and flow to form the sleek, glossy and lustroussurfaces. And, naturally those other areas which possess the higher meltviscosities and the polymerized or cross-linked monomers resist thehigher temperatures and do not soften, melt or flow but retain theirflat, dead or dull mat surface finish or texture. The temperature of theentire assembly must reach the fusion temperature of the resins in orderto obtain the desired maximum strength. Fusion is normally obtained at atemperature of from about 325° F. to about 470° F., depending upon theparticular polymeric product being used. Such temperature also must besufficient as to activate or decompose the particular blowing or foamingagent which is present in the plastisol. It is again to be observed thatblowing and foaming temperatures, as well as fusion and gellingtemperatures, are ambient air temperatures and not temperatures of theproduct exposed to such ambient air temperature.

Reference to the drawings, and particularly to FIGS. 2 and 3 thereofwill clarify the actions which take place during such blowing andfoaming procedures. The plastisol or the originally potentially foamableresinous polymer composition initially contained a blowing or a foamingagent therein, such as azodicarbonamide, which was substantiallyuniformly distributed therein. However, those portions of the printingink composition 18 lying in zones A additionally contained a blowing orfoaming modifier, such as an inhibitor, and hence those portions of theresinous polymer composition lying thereunder in zones A are relativelyunblown or unfoamed due to the inhibiting action of the blowing orfoaming inhibitor. On the other hand, those portions of the printing inkcomposition 18 lying in zones B did not contain any blowing or foamingmodifier, such as an inhibitor, and hence such portions of the resinouspolymer composition lying thereunder in zones B are relatively blown orfoamed substantially completely. Such actions are well described in thepreviously mentioned United States Patents.

Additionally, those portions of the printing ink composition 18 in zonesA also contained a free-radical polymerization initiator or organicperoxide which was activated or decomposed during the embossingoperation to polymerize and/or cross-link the reactive polymerizablemonomer in the wear layer 22 and to increase the melt viscosities ofsuch portions. As a result, such portions retained their flat, dead ordull mat finish or texture throughout the blowing or foaming operation.On the other hand, however, those portions of the printing inkcomposition 18 in zones B did not contain any free-radicalpolymerization initiator or organic peroxide and there was nopolymerization or cross-linking of the polymerizable monomer in the wearlayer thereover and the melt viscosities of such portions did notincrease. As a result, such portions were not able to resist theelevated temperatures of the blowing and foaming cycle, and they melted,softened and flowed to form sleek, glossy and lustrous surfaces in suchzones B.

With further reference to the development of the sleek, glossy, orlustrous finish, as compared to the retention of the flat, dead or dullfinish, the following numerical comparative gloss levels and rangesshould exist for the satisfactory application of the principles of thepresent inventive concept.

The sleek, glossy or lustrous finish areas should have gloss levels inthe range of from about 15 to about 90, or even higher; the flat, deador dull mat finish areas should have gloss levels in the range of fromabout 70 down to about 3, or even less; with the differences in thegloss levels between the two contrasting finishes being in the range ofat least about 10 in gloss level ranges below 50 and at least about 20in gloss level ranges equal to or above 50. Such numerical gloss levelvalues are determined by the procedures set forth in A.S.T.M. 523-67(1972) at an angle of 60°.

It is also to be observed that reference to sleek, glossy or lustrousfinishes, as compared to flat, dead or dull mat finishes, is merely atypical or preferred embodiment of the present inventive concept. Theseterms or phrases are comparative or relative terms or phrases and areused merely or primarily to indicate differences in gloss levels.

For example, the principles of the present inventive concept are equallyapplicable to the obtaining of a sleek, glossy or lustrous finish insome certain selected areas and the obtaining of even more sleek, glossyor lustrous finishes in certain other selected areas, again keeping thedifferences in the gloss level values greater than about 20, inasmuch asthe gloss levels involved in such embodiment will be greater than about50.

Such sleek and very sleek contrasts may be obtained by omitting themechanical embossing procedure with a roughened surface and bysubstituting therefor a platen-pressing or press-rolling operation witha very smooth, highly polished surface, whereby the entire surface ofthe resinous wear layer is given an extremely smooth, sleek, shiny,glossy or lustrous finish.

High temperatures and pressures are subsequently similarly employed, aspreviously described in connection with the blowing and foaming step,whereby the polyfunctional reactive polymerizable and cross-linkablemonomers in the wear layer lying over the polymerization andcross-linking initiators in the printing ink composition, having beencross-linked during the heated platen-pressing or press-rollingoperation, effectively resist such heating and pressure and "freeze"those particular areas, whereby they are capable of retaining theirextremely sleek, shiny, glossy or lustrous finish throughout suchsubsequent blowing or foaming operation.

However, those other areas which contain the monomeric materials notlying over any polymerization or cross-linking initiators or organicperoxides still contain such monomeric materials in unpolymerized andun-cross-linked state and hence, soften, melt and flow and thus losesome of their extremely sleek, shiny, glossy or lustrous finish but dodevelop or retain sufficient of their previous extremely sleek, shiny,glossy or lustrous finish at least about 20 units in gloss level, lessthan the gloss level of the extremely sleek, shiny, glossy or lustrousfinish.

Reference to FIGS. 1 through 3 of the drawings for comparative purposesonly would therefore indicate that the use of the alternative proceduresdescribed in the preceding few paragraphs would have areas "B" as sleek,glossy or lustrous, whereas areas "A" would be even more sleek, glossyor lustrous.

THE BARRIER COAT

In some cases, it has been found that the blowing or foaming action ofthe potentially foamable plastisol is of such a strong and vigorousnature that the gases which are developed or liberated by the blowing orfoaming agent tend to escape upwardly from the heated plastisol and tendto enter the wear layer to undesirably affect the smoothness andevenness of the wear layer surface and particularly those areas thereofhaving a low melt viscosity, or substantially no polymerized and/orcross-linked monomers therein, or sleek, glossy or lustrous surfaces.Such could be ruinous to the smoothness of such surfaces and would beundesirable from an esthetic viewpoint. Additionally, such affects thestrong contrast between the sleek, glossy or lustrous surfaces and theembossed, flat, dead or dull surfaces adjacent thereto.

This undesirable effect can be avoided by placing a relatively thinbarrier coat or layer having a thinness of only about 6 mils or less,down to about 1 or 2 mils, on top of the potentially foamable plastisolbefore the printed pattern or design is applied thereto, oralternatively such a barrier coat is applied over the printed pattern ordesign before the application of the wear layer. Such a barrier coat orfilm effectively prevents the gases from escaping upwardly from theblowing or foaming plastisol and entering the wear layer. The barrierlayer is applicable as a film but is normally applied as a plastisolresinous polymer composition in a thin layer of a resin such as a vinylchloride polymer or copolymer having a relatively very high molecularweight. Gelling of such a plastisol barrier layer naturally follows atan elevated temperature below the activation or decomposing temperatureof the blowing or foaming agent and the polymerization initiator ororganic peroxide.

The thickness of the barrier coat or layer must not be that great as toprevent the blow modifier or inhibitor from exerting its blow modifyingor inhibiting effects downwardly through the barrier layer into theplastisol during the blowing operation or the polymerization initiatorfrom exerting its effects upwardly during the polymerization and/orcross-linking of the reactive polymerizable monomers.

A few preferred and typical barrier coat formulations are as follows:

    ______________________________________                                        (Parts by weight, based on 100 parts by weight of resin, phr)                                       BC-1   BC-2                                             ______________________________________                                        Polyvinyl chloride, high molecular weight,                                    dispersion grade, inherent viscosity 1.4                                                              89       90                                           Polyvinyl chloride, high molecular weight,                                    blending resin, inherent viscosity 0.9                                                                11       10                                           Dioctyl phthalate                6                                            Epoxidized soya oil     5        5                                            2,2,4-trimethyl-1,3-pentanediol diisobutyrate                                                         6.9      8.8                                          Butyl benzyl phthalate  29       19.6                                         Polydodecyl benzene     8.5      5.5                                          Ba-Zn phosphite stabilizer                                                                            7.25     3                                            UV absorber             0.32     0.32                                         Toner                   p.01     0.01                                         ______________________________________                                    

Other additives and agents, such as, for example, ethoxylatednonylphenol, a viscosity depressant, or other plasticizers andstabilizers solvents or diluents, fillers, etc., can be used.

THE MODIFICATION OF FIGS. 4 AND 4A

It has been previously stated herein that the base layer or substrate 11may comprise simply a fibrous backing sheet material and that otherlayers, such as non-foamable or potentially foamable resinous polymercompositions or plastisols or other sheet materials may be omitted.

Such a modification is illustrated in FIGS. 4 and 4A which depict,respectively, the resinous polymer sheet material before and after thecompletion of the embossing and subsequent heating steps in itsmanufacture. In these Figures, there is shown a resinous polymer sheetmaterial 30 comprising a relatively flat backing sheet material 32 offibrous nature, such as an asbestos felt upon which is printed aprinting ink composition 38 in the form of a desired pattern or designin a plurality of colors, as usual. If necessary, a smoothing orleveling resinous polymer coating, such as an acrylic coating, may beapplied to the asbestos felt 32, if its surface is too uneven, hairy,fibrous, or irregular before the printing of the printing inkcomposition 38 thereon. No blow modifiers or inhibitors are included inany portion or color of the printed pattern or design. However, afree-radical polymerization initiator or organic peroxide is included inthe portions 40 of the printed pattern or design, whereas nofree-radical polymerization initiator or organic peroxide is included inthe portion 41. A wear layer 42 is then applied to the surface of theprinted pattern or design in the usual way and contains thereinpolymerizable reactive monomers substantially uniformly. The wear layer42 is then embossed in overall fashion under sufficient pressure and ata sufficiently elevated temperature for a sufficiently long period oftime as to create on its surface the desired finish or texture, such asa flat, dead or dull mat finish or texture.

During such mechanical embossing, the reactive polymerizable monomers inthe wear layer 42 are polymerized and/or cross-linked and the meltviscosity is increased but only in those portions thereof which liedirectly over the free-radical polymerization initiator or organicperoxide in the printing ink composition. All other areas which do notlie over any free-radical polymerization initiator or organic peroxidedo not have any polymerized and/or cross-linked monomers in the wearlayer and the melt viscosity of such areas is also substantiallyunchanged.

As a result, when the mechanically embossed sheet material is raised toan even more elevated temperature, somewhat similar to the temperaturewhich would exist under blowing or foaming conditions, the polymerizedand/or cross-linked portions of the wear layer which also haverelatively higher melt viscosities, are able to resist the softening andthe melting effects of such heating and retain their mechanicalembossment and remain flat, dead or dull mat in appearance. However, theother areas which have not been polymerized and/or cross-linked and donot possess relatively higher melt viscosities, soften, melt and flowtogether to form a sleek, glossy and lustrous appearance.

The relatively flat, dead or dull mat finish or texture is designated inFIG. 4A by the reference letter A and it is to be noted that such areasare in complete and precise registry with the areas 40 containing thefree-radical polymerization initiator or organic peroxide and with theparticular color of the printed pattern or design containing suchmaterial. Also, the relatively sleek, glossy or lustrous surfaces aredesignated by the reference letter B and are over areas of the printingink composition which do not contain any free-radical polymerizationinitiator or organic peroxide and thus in complete and precise registrywith such areas which contain different colors of the printed pattern ordesign. Small protuberances are noted in the surface of the wear layer42 in the zones A. These will be discussed in greater detailhereinafter.

THE MODIFICATION OF FIGS. 5 AND 5A

It has also been stated herein that the base layer or the substrate 11may comprise simply a resinous polymer composition and that otherlayers, such as a relatively flat, fibrous sheet material, or othersheet materials may be omitted. Such a modification is shown in FIGS. 5and 5A which depict, respectively, the resinous polymer sheet materialsbefore and after the completion of the mechanical embossing step and theblowing or foaming procedure. In these Figures, there is shown aresinous polymer sheet material 50 comprising a relatively flat andrelatively thin sheet of release paper 55 of a conventional character asare commercially available. Upon such release paper 55 is deposited orlaid down a layer of a potentially foamable resinous polymer composition53 which contains a conventional blowing or foaming agent such asazodicarbonamide. The surface of the potentially foamable plastisol 53is gelled and is then printed with a printing ink composition 58 whichcontains a free-radical polymerization initiator or organic peroxide anda particular pigment or color in areas 60, whereas other areas 61 do notcontain any free-radical polymerization initiator or organic peroxidebut do contain a different pigment or coloring agent. No blow modifiersor inhibitors are included in any portion of the printing inkcomposition 58.

A wear layer 62 is then applied to the surface of the printing inkcomposition 58 and contains substantially uniformly therein quantitiesof a reactive polymerizable monomer. The wear layer is then embossedmechanically under sufficient pressure and at a sufficiently elevatedtemperature and for a sufficiently long period of time as to createthereon the desired flat, dead or dull mat finish or texture in anoverall pattern of embossment, during which time the reactivepolymerizable monomer is normally polymerized and cross-linked.

A conventional blowing or foaming operation then follows at an even moreelevated temperature whereby the blowing or foaming agent causes theexpansion of the resinous polymer composition. Such expansion is wellshown in FIG. 5A. At the same time, the highly polymerized orcross-linked monomers in the areas 60, which areas also possess highermelt viscosities, resist the softening or melting effects of the heatduring the blowing and foaming operation and such areas 60 remain in adesired flat, dead or dull mat finish or texture. However, the areas 61which do not lie over any portions of the printing ink composition 58which contain any free-radical polymerization initiator or organicperoxide are not polymerized or cross-linked and do not have higher meltviscosities and are unable to resist the softening or melting tendenciescreated during the heating of the blowing and foaming cycle and hencesuch areas melt and flow together to form a sleek, glossy or lustroussurface which contrasts sharply with the flat, dead or dull mat finishor texture of the areas 60. Areas A are again flat, dead or dull,whereas areas B are sleek, glossy or lustrous.

Inasmuch as no blowing or foaming modifiers or inhibitors were presentin the printing ink composition, the blowing or foaming is uniform andno chemically embossed effects are realized on the surface of the wearlayer. Small protuberances are noted in the surface of the wear layer 62in zones A. These will be discussed in greater detail hereinafter. Therelatively flat and relatively thin sheet of release paper is removedfrom the bottom surface of the resinous polymer composition subsequentto the blowing or foaming cycle. However, if the resinous polymercomposition, printing ink composition, and wear layer possess sufficientstrength as to permit the handling thereof, or if another carrier issupplied therefor, then the release paper may be removed prior to theblowing and foaming operation.

Additionally, the resinous wear layer 62 may have incorporatedsubstantially uniformly therein a polymerization initiator or organicperoxide which is activatable or decomposable at an even highertemperature than the decomposition or activation temperature of thepolymerization initiator or organic peroxide in the printing inkcomposition 58.

Thus, after the polymerization and/or cross-linking of the reactivepolymerizable monomer in zones A is substantially complete, then, theambient air temperature may be increased to obtain the followingresults. Zones A which contain polymerized and/or cross-linked monomersand have higher melt viscosities retain their appearance and theirprotuberances. Zones B develop their sleek, glossy or lustrousappearance, as before. Thus far, only the polymerization initiator inzones A have been activated and/or decomposed. The polymerizationinitiator or organic peroxide in the wear layer has not been activatedor decomposed as yet because it possesses a higher activationtemperature. But, when the temperature is sufficiently elevated as tobring about blowing or foaming, then the polymerization initiator ororganic peroxide in the wear layer is activated or decomposed, wherebyall the reactive polymerizable monomer in the wear layer, including thezones B, are polymerized and/or cross-linked.

The result is that the surface of the wear layer 62 in zones A has anembossed, flat, dead or dull textured finish, whereas the surface of thewear layer 62 in zones B has a sleek, glossy or lustrous finish but bothzones A and B contain high concentrations of polymerized and orcross-linked reactive polymerizable monomers and both portions haverelatively high melt viscosities.

THE MODIFICATION OF FIGS. 6 AND 6A

In FIGS. 6 and 6A, there is illustrated still another modification ofthe principles of the present inventive concept. There is shown aconventional base layer or substrate comprising a relatively flat,fibrous backing sheet material 72 such as an asbestos felt, upon whichis applied a printing ink composition 78 in the form of a desiredmulti-colored pattern or design wherein certain predetermined portionsor colors 80 contain a free-radical polymerization initiator or organicperoxide and a particular pigment or coloring agent. Other predeterminedprinted portions 81 of the printing ink composition 78 on the surface ofthe fibrous backing sheet material 72 contain no free-radicalpolymerization initiator or organic peroxide but do contain a differentpigment or coloring agent. Inasmuch as there is no potentially foamableplastisol involved, there is no need for a blowing or foaming modifieror inhibitor in the printing ink composition 78 or in any portionthereof.

An upper wear layer 82 comprising a resinous polymer composition is thenapplied to the surface of the printing ink composition 78 and containssubstantially uniformly therein a reactive polymerizable monomericmaterial. The wear layer 82 is then heated to a relatively lowtemperature in order to gel and harden or firm its surface and tofacilitate its subsequent handling and processing. No mechanicalembossing of any type takes place on the surface of the wear layer 82,and in this respect it differs from the modification previouslydiscussed with reference to FIGS. 4 and 4A.

Upon the application of sufficient heat to elevate the temperature ofthe resinous polymer material sufficiently to activate or decompose thefree-radical polymerization initiator or organic peroxide,polymerization and cross-linking of the reactive polymerizable monomericmaterials in the wear layer takes place, along with a correspondingincrease in the melt viscosity of those areas 83 which are positioneddirectly over the free-radical polymerization initiator or organicperoxide in the printing ink composition 78. However, in the areas 81which do not overlie any free-radical polymerization or cross-linking ofthe reactive polymerizable monomeric materials in the wear layer 82 andthere is no concomitant increase in the melt viscosity in the areas 81.

Moreover, with respect to the areas 83 wherein there is polymerizationand/or cross-linking along with increased melt viscosity, there iscreated an unusual and distinct embossed effect which causes the surfaceof the wear layer 82 to be raised or elevated to a higher level as muchas about 5 mils or even more. Such raised or elevated effect not notedto any degree whatsoever in the areas 81 and the combined embossedeffect of the raised portions in zones A as contrasted to the normalportions in zones B is esthetically excellent. Such raised or elevatedprotuberances which are also noted in other embodiments of theinvention, may be as small as about 1 or 2 mils but are very noticeable.The precise reason for such an unusual effect is not fully or completelyunderstood but it is believed to be caused by the differences inpolymerization and/or cross-linking and melt viscosities in the twozones. In any event, even the smallest of the protuberances can be feltby the finger and observed by the naked eye.

THE MODIFICATION OF FIG. 7

In FIG. 7, there is illustrated a still further modification of theprinciples of the present inventive concept. There is shown a resinouspolymer sheet material 90 comprising a conventional, relatively flat,fibrous sheet material 92 such as an asbestos felt. Applied to thefibrous backing sheet material 92 is a layer of a resinous polymercomposition 94 which is shown in the blown condition due to the priorinclusion therein of a conventional blowing or foaming agent, such asazodicarbonamide, which was activated and decomposed by exposure to heatat a sufficiently elevated temperature for a sufficient period of time.

A barrier coat or layer 95 is situated atop the blown cellular resinouspolymer composition 94 and serves to prevent any of the gases developedand liberated during the blowing and foaming operation from escaping. Aprinting ink composition 98 is applied to the surface of the barriercoat 95 in the form of a multi-colored pattern or design. Portions ofthe printed pattern or design contained a free-radical polymerizationinitiator or organic peroxide in areas 93, whereas certain other areasdid not contain any free-radical polymerization initiator or organicperoxide.

No blow modifier or inhibitor is included in any portion of the printingink composition 98 and hence the blowing or foaming is uniform and thereis no chemical embossing of the top surface of a wear layer 91 which isapplied to the top of the printing ink composition 98. The entiresurface of the wear layer 91 was previously embossed mechanically butsuch embossment has disappeared from zones B and is evident only inzones A. Protuberances, as discussed previously hereinbefore, are againnoted in zones A and can easily be felt by the finger and observed bythe naked eye, especially when multi-colored patterns or designs areused.

Such difference in appearance, of course, is caused by the fact that thefree-radical polymerization initiator or organic peroxide in zones Acaused a polymerization and/or cross-linking of the reactivepolymerizable monomeric material in the wear layer 91, along with anincrease in the melt viscosity thereat, whereby the mechanicalembossment in such zones survived the heating at the elevatedtemperatures of the blowing and foaming cycle. However, in zones Bwhereat there was no free-radical polymerization initiator or organicperoxide in the printing ink composition 98, there was correspondinglyno polymerization and/or cross-linking of the reactive polymerizablemonomeric materials in the wear layer 91, and there was no increase inthe melt viscosity in such zones B. As a result, such areas were notable to resist the softening, melting and flowing tendencies created bythe elevated temperatures during the blowing and foaming cycle. Suchareas B are no longer embossed mechanically and they are no longer flat,dead or dull mat finished or textured but have become sleek, glossy andlustrous in appearance.

The net effect is somewhat similar to that achieved in the product ofFIGS. 1-3, with the major exception that the resinous polymercomposition in FIG. 7 did not have its blowing or foaming actionmodified or inhibited by the presence of any blow modifier or inhibitorin the printing ink composition but was allowed to blow and foam toexpand evenly and uniformly. In FIGS. 1-3, the blow modifier orinhibitor brought about the embossed effect of the chemical embossingprocedure.

THE MODIFICATION OF FIG. 8

In FIG. 8, there is illustrated another modification of the basicprinciples of the present inventive concept. There is shown therein aresinous polymer sheet material 100 comprising a conventional,relatively flat, fibrous sheet material, such as an asbestos felt.Applied to the fibrous backing sheet material 102 is a layer of aresinous polymer composition 104 which is shown in an unblown orunfoamed state inasmuch as there was no blowing or foaming agentoriginally included in the plastisol composition. In the absence ofblowing or foaming, the resinous polymer composition is non-cellular inthe final product.

No barrier coat is employed in such a modification and none is neededinasmuch as there is no gas development or liberation in the plastisolduring the heated fusion operation at the elevated temperature. Aprinting ink composition 108 is applied to the surface of the resinouspolymer composition 104 in the form of a multi-colored pattern ordesign. Portions of the printing ink composition 108 contain afree-radical polymerization initiator or organic peroxide, such as inareas 103, whereas other portions of the printing ink composition 108 donot contain any free-radical polymerization initiator or organicperoxide, as in areas 106.

Inasmuch as there is no blowing or foaming agent in the resinous polymercomposition, the final height of the resinous polymer sheet material 100is considerably less than that of FIG. 7 which, as noted previously, didcontain a blowing or foaming agent, such as azodicarbonamide, in itsresinous polymer composition 94. The mechanically embossed dead or dull,flat mat texture of the areas 103 (zones A) still are retained, whereasthe areas 106 (zones B) have lost their flat, dead or dull mat textureand have become sleek, glossy and lustrous as a result of the heatedfusion operation.

Such difference in appearance is caused by the fact that thefree-radical polymerization initiator or organic peroxide in zones Acaused a polymerization and/or cross-linking of the reactivepolymerizable monomeric material in the wear layer 101, along with anincrease in the melt viscosity thereat, whereby the mechanicalembossment in such zones A survived the heating at the elevatedtemperatures of the fusion cycle. However, in zones B whereat there wasno free-radical polymerization initiator or organic peroxide in theprinting ink composition 108, there was correspondingly nopolymerization and/or cross-linking of the reactive polymerizablemonomeric materials in the wear layer 101, and there was no increase inthe melt viscosity in such zones B. As a result, such areas 106 were notable to resist the softening, melting and flowing tendencies created bythe elevated temperatures during the fusion of the resins. Such areas Bare no longer mechanically embossed and they are no longer flat, dead ordull mat finished but have become sleek, glossy and lustrous.

The net effect is somewhat generally similar to that achieved in theproduct of FIG. 7, with the major exception that the product of FIG. 7is blown and foamed, whereas the product of FIG. 8 is not blown orfoamed. The surface of the wear layer, however, is very similar in bothFIGS. 7 and 8, only the chemical embossment is different. Raised orelevated protuberances are again observed in zones A as before.

A FURTHER MODIFICATION

Thus far in this disclosure, the major emphasis has been placed onincorporating free-radical polymerization initiator and the blowingmodifier or inhibitor in the same printed portion of the printed patternor design of the printing ink composition, when both are to be used inthe manufacture of the resinous polymer sheet material product. This isnot always necessarily so. If desired, a free-radical polymerizationinitiator may be incorporated in one portion of the printed pattern ordesign and a blowing modifier or inhibitor may be incorporated inanother portion of the print or design.

Preferred and typical printing ink compositions for such a modificationare as follows:

    ______________________________________                                                                    Parts                                             ______________________________________                                        Solution grade copolymer of vinyl chloride (90 parts)                         and vinyl acetate (10 Parts)  15                                              Methyl ethyl ketone           83                                              Dicumyl peroxide polymerization initiator                                                                    2                                              Pigment or coloring material, as desired or required                          Solution grade copolymer of vinyl chloride (90 parts)                         and vinyl acetate (10 parts)  14                                              Methyl ethyl ketone           66                                              Trimellitic anhydride inhibitor                                                                             20                                              Pigment or coloring material, as desired or required                          ______________________________________                                    

One preferred and typical final product ultimately is obtained and isstructurally similar to the final product illustrated in FIGS. 2 and 3of the drawings. Thus, if the trimellitic anhydride inhibitor isincorporated in zones A, the lower surfaces of the wear layer thereoveras shown in FIGS. 2 and 3, do not retain the mechanically embossmentimpressed thereon and are sleek, glossy or lustrous. And, if the dicumylperoxide polymerization initiator is incorporated in zones B, the highersurfaces of the wear layer thereover, as shown in FIGS. 2 and 3, retainthe mechanical embossment impressed thereon and are flat, dead or dull.Thus, the final product is visually different from the final productwhich is obtained in FIGS. 2 and 3.

The structure of the product of this embodiment would be identical tothe structure of the product illustrated in FIGS. 2 and 3, except forthe reversal of the sleek, glossy or lustrous finish areas and the flat,dead or dull texture areas. Again, the portions of the wear layer lyingover the polymerization initiator are relatively highly polymerized andcross-linked and have relatively high melt viscosities, whereas theportions of the wear layer lying over the blowing modifier or inhibitorare relatively low in polymerized or cross-linked monomer and haverelatively low melt viscosities.

Such a reversal of surface visual effects is not desirable in simulatedceramic tile patterns or designs in most cases, wherein it is normallydesired that the higher lands be sleek, glossy or lustrous and the lowermortar areas be flat, dead or dull, but is desirable in other patternsor designs wherein a greater diversification of visual effects isdesired or required.

It is not essential that certain predetermined portions or colors of theprinted pattern or design contain desired or required concentrations ofthe polymerization initiator or organic peroxide and that certain otherpredetermined portions or colors of the printed pattern or designcontain absolutely no concentrations of the polymerization initiator ororganic peroxide.

The polymerization initiator or organic peroxide may be contained inseveral different portions or colors of the printed pattern or design inseveral different concentrations. With the proper selection of desiredvarying concentrations several varying gradations of surface finishes ortextures may be obtained. Sharpness of individual contrast may belessened to some degree but a much greater variety of effects, finishesand textures is thus available.

Such variations and gradations of surface finishes and textures is alsoobtainable by the use of several different polymerization initiators ororganic peroxides having several different levels or degrees of activityor several different temperatures of activation or decomposition.Polymerization initiators or organic peroxides which have greateractivity tend to polymerize the reactive polymerizable monomers to agreater degree and to increase the melt viscosity of the correspondingportions of the wear layer to a greater extent, whereby greaterresistance is created to the melting, softening and flowing effectsduring the blowing and foaming cycles. Thus, the placing of a highactivity polymerization initiator or organic peroxide in one area of theprinted pattern or design will tend to maintain the embossed flat deador dull mat finish applied during the embossing procedure, whereas theplacing of a low activity polymerization initiator or organic peroxidein a different area of the printed pattern or design will tend to permitthe embossed flat dead or dull finish or texture to partially disappearto yield a different texture and/or gloss level or degree for the sleek,glossy or lustrous finish. Thus multiple mat and gloss and multiplefinish and texture levels are obtainable.

In addition to the use of a plurality of polymerization initiators ororganic peroxides in a plurality of different portions or colors of theprinted pattern or design of the printing ink composition, an additionaleffect is obtainable by including an additional polymerization initiatoror organic peroxide having a relatively high temperature of activationor decomposition in the wear layer in a substantially uniform matter.

Thus, it can be arranged that the several different polymerizationinitiators or organic peroxides may be activated or decomposed atseveral different stages of the procedure whereby several differentfinishes or textures may be obtained. Then, at a much later stage, suchas, for example, during the blowing and foaming cycle, the hightemperature polymerization initiator or organic peroxide may then beactivated to polymerize and/or cross-link the reactive polymerizablemonomers in the entire resinous wear layer. Such would tend to increasethe melt viscosities of all the different areas of the resinous wearlayer as an overall effect.

AN ALTERNATIVE PROCEDURE

An alternative "upside-down" procedure for making the resinous polymersheet materials of the present invention is as follows: a resinous wearlayer, such as described previously herein, is cast upon or otherwiseformed on a suitably textured or embossed surface, such as a coarselytextured, parchment-type release paper, or other roughened, uneven,crinkled, rugose, or bumpy surface, or any similar or like protuberantor irregular surface having release properties and characteristics givento it.

The resinous wear layer composition is sufficiently fluid as to flowinto and completely fill all the nooks and crannies, recesses and nichesof the textured or embossed surface and thus to assume surface featuresand characteristics substantially identical thereto. Such a surface,being so irregular, uneven, pebbly or grainy that it does not reflectlight regularly but more or less scatters it, would present a flat, deador dull mat textured or embossed appearance to the eye, if the releasesurface were to be removed therefrom so that one could see the shapedsurface of the resinous wear layer composition.

A printing ink composition, or a plurality of such compositions, such asdescribed previously herein, is applied or otherwise deposited on thesurface of the cast resinous wear layer composition, after it has beengelled by conventional and standard procedures. A desired design orpattern is thus applied, and, as described previously herein, certainpredetermined areas of the printed pattern or design containpolymerization initiator or organic peroxide and, if desired, also ablowing or foaming modifier or inhibitor, whereas other predeterminedareas of the printed pattern or design contain either (1) nopolymerization initiator or organic peroxide at all, or (2) a differentconcentration of the same polymerization initiator or organic peroxide,or (3) a different polymerization initiator or organic peroxide having adifferent level or degree of activity or a different temperature ofactivation or decomposition. The printing ink composition is then dried.

A resinous barrier coat, such as described previously herein, may thenbe applied to or otherwise deposited on the dried printed pattern ordesign of the printing ink composition.

Heating the printing ink composition and polymerization initiator ororganic peroxide contained therein and the resinous wear layer to asufficiently elevated temperature then takes place, whereupon thepolymerization and/or cross-linking of the reactive polymerizablemonomer in the resinous wear layer takes place in selected predeterminedportions thereof lying under the polymerization initiator or organicperoxide. No polymerization and/or cross-linking of the reactivepolymerizable monomer, however, takes place in those portions of theresinous wear layer not lying under any polymerization initiator ororganic peroxide. And, at the same time, the polymerized and/orcross-linked portions of the resinous wear layer developed increasedhigher melt viscosities. Additionally, gelling of the resinousplastisols takes place whereby further handling and further processingis made easier.

A base layer or substrate preferably comprising a relatively flat,fibrous backing sheet of asbestos fibers, such as described previouslyherein, and a potentially foamable resinous polymer composition, such asa polyvinyl chloride plastisol, also as described previously herein isthen laminated or otherwise adhered to the surface of the barrier coat,preferably under pressure and at elevated temperatures in a laminator,to form a unitary, integral structure.

The strippable coarsely textured release surface upon which the resinouswear layer was originally cast or formed is then removed and reveals asuitable textured or embossed surface on the resinous wear layer,precisely corresponding to the textured or embossed surface of therelease material.

Heating to an even more elevated temperature in a fusion or blowing orfoaming oven atmosphere brings about several actions. Those portions ofthe resinous wear layer which do not contain any polymerized and/orcross-linked reactive polymerizable monomers and which do not possessrelatively high melt viscosities soften and melt at such temperaturesand flow to form a sleek, glossy or lustrous surface or finish, whereasthose other portions of the resinous wear layer which do containpolymerized and/or cross-linked reactive polymerizable monomers andwhich possess relatively higher melt viscosities are able to resist thesoftening and melting tendencies at such elevated temperatures and donot flow but maintain their original textured or embossed flat, dead ordull surfaces.

At the same time, if a blowing or foaming agent, such asazodicarbonamide, was contained in the potentially foamable resinouspolymer composition of the base layer or substrate, then blowing orfoaming thereof takes place. And, if a blowing modifier or inhibitor wasalso included in the printed pattern or design of the printing inkcomposition, then the blowing or foaming action will be correspondinglymodified or inhibited.

The final product is, of course, substantially similar to the finalproduct obtained in the previously described methods but possesses theprocedural advantage that no separate mechanical embossing step isrequired.

In this alternative "upside-down" procedure, it is noted that theresinous barrier coat is applied to the dried printed pattern or designof the printing ink composition, prior to the heating of the printingink composition and the polymerization initiator therein and theresinous wear layer and the reactive polymerizable monomer therein tobring about the polymerization and/or cross-linking of the reactivepolymerizable monomer. This is merely a preferred or typical method. Theresinous barrier coat may be omitted completely or, if desired, it maybe applied or otherwise adhered to the resinous wear layer prior to theapplication of the printed pattern or design. The important function tobe realized is that the polymerization initiator in the printing inkcomposition be able to bring about the polymerization and/orcross-linking of the reactive polymerizable monomer and that the barriercoat is present, if needed, when the potentially foamable resinouspolymer composition is subsequently blown or foamed and the generatedgases are released.

A special note is deemed to be advisable with respect to the citation oftemperatures and temperature ranges in this disclosure. Whenevermaterial is being heated by being passed through a heated oven or otherheating device, and the temperature of such a heated oven is maintainedat a desired temperature, it is to be appreciated that the material doesnot reach that temperature, particularly if it is in such a heatedenvironment for only a very short period of time. The temperature of thematerial is usually some degrees less than the temperature of thesurrounding heated environment. Such a situation normally exists duringa gelling operation of the plastisol when the plastisol is passedthrough a heated environment containing heated air.

On the other hand, whenever material is being pressed against a heatedsurface, such as a heated platen or other pressing device, and a veryintimate contact is established between the heating element and thematerial to be heated, then the temperature of the material being heatedwill approach substantially the temperature of the heating source. Sucha situation normally exists during a mechanical embossing operationwherein a heated platen or other embossed heated surface is pressed invery intimate contact with the material which is to be mechanicallyembossed. This is especially true if the heaed platen or die is pressedagainst the surface of the material being heated and embossed underapplied pressure, which in the present case may be in the range of up to200 pounds per square inch gauge.

THE MODIFICATIONS OF FIGS. 9-12

Thus far, the emphasis of the present invention has been placed on theconcept of providing certain surface portions of the wear layer with aflat, dead of dull mat finish, such as is created by the mechanicalembossing, and certain other surface portions of the wear layer withanother contrasting texture or effect, such as a sleek, glossy, orlustrous finish, such as is created in the heated fusion oven. In somecases, it may be desirable that substantially the entire surface portionof the wear layer retain the textured finish created by the mechanicalembossing operation. Such overall effect may be achieved by severalprocesses, such as illustrated in FIGS. 9-12 of the drawings.

In FIG. 9, there is illustrated a resinous polymer sheet material 110comprising a typical, relatively flat, backing web or sheet material112, similar to the backing sheet material 12 described previously. Arelativey flat, substantially uniform layer of a potentially foamable(or non-foamable) resinous polymer composition 113, similar topreviously described potentially foamable (or non-foamable) resinouspolymer composition layer 13, is formed on or is applied to the backingsheet material 112.

Such resinous polymer composition 113 is then processed as describedpreviously herein, including, for example, a heating, gelling andfirming, and cooling operation, and is printed or coated with a suitableprinting ink composition 118 having a desired pattern or design ofvarious colors, such as 118a, 118b, 118c, 118d, and 118e.

Now, whereas in previous embodiments of the invention, some of theseprinted colored portions or areas contained certain amounts ofpolymerization initiators, catalysts, or organic peroxides, and otherprinted colored portions or areas contained different amounts or nopolymerization initiators, catalysts, or organic peroxides at all, allof the colors, portions or areas of the printed pattern or design ofFIG. 9 contain like amounts and equal concentrations of the samepolymerization initiators, catalysts, or organic peroxides.

If desired, such as when a blowing or foaming operation is employedsubsequently a relatively thin barrier coat or layer 115, such as thepreviously described barrier coat or layer, may be placed over thepotentially foamable resinous polymer composition 113, either before theprinted pattern or design 118 is applied thereto, or, as shown in FIG.9, after the printed pattern or design is applied to the resinouspolymer composition 113. The purpose of such a barrier coat or layer hasbeen described previously herein.

A relatively uniform thin wear layer 122 containing one or more reactivepolymerizable monomeric materials, such as the previously described wearlayer 22, is then applied to the printed, gelled and cooled potentiallyfoamable resinous polymer composition 113. Gelling and firming of thewear layer 122 take place, as described previously, followed by anover-all mechanical embossing procedure also as described previously.

Inasmuch as the entire surface of the wear layer 122 lies over somepolymerization initiators, catalysts, or organic peroxides in theprinting ink composition 118, polymerization and cross-linking of thereactive polymerizable monomeric materials takes place substantiallyuniformly throughout the wear layer 122, along with increased meltviscosities also being uniformly created throughout the wear layer 122during the mechanical embossing.

Heating and fusion, as well as blowing or foaming (if a blowing orfoaming agent was included originally in the resinous polymercomposition 113), take place as described previously. The mechanicalembossing of the surface of the wear layer 122 is retained substantiallyuniformly throughout, even after such operations.

FIG. 10 shows a relatively flat, resinous polymer sheet material 120comprising: a fibrous backing layer 112; a printing ink composition 118uniformly containing a polymerization initiator, catalyst, or organicperoxide; a barrier coat or layer 115; and a wear layer 122, allsubstantially as described previously with particular reference to FIG.9. A resinous polymer composition 123 is employed which contains ablowing or foaming agent. The previously described procedures ofheating, gelling and firming of the resinous polymer composition 123 andof the wear layer 122, along with the subsequent overall mechanicalembossing of the surface of the gelled wear layer 122, and the otherpreviously described procedures take place, followed by conventionalheating and fusion, and blowing or foaming in a fusion oven. FIG. 10illustrates the blown resinous polymer sheet material 123, subsequent tothe heating, fusion and blowing or foaming operations. The mechanicalembossing on the surface of the wear layer 122 is retained substantiallyuniformly throughout.

FIG. 11 shows a relatively flat, resinous polymer sheet material 130comprising: a fibrous backing layer 112; a resinous polymer composition133 containing a blowing or foaming agent; a printing ink composition138 substantially uniformly containing equal concentrations and amountsof a free radical polymerization initiator, catalyst, or organicperoxide in all portions of areas thereof, as well as a blowing orfoaming modifier or inhibitor which is contained only in certainselected portions or areas thereof 138a of the printing ink compositionlayer 138; a relatively thin barrier coat or layer 115; and a resinouspolymer wear layer 122 which contains a reactive polymerizable monomericmaterial substantially uniformly therein.

A blowing or foaming agent has been uniformly included in the resinouspolymer composition 133 and it is heated and fused and blown or foamed,as illustrated. However, due to the presence of the blowing or foamingmodifier or inhibitor which is present in certain selected portions orareas 138a of the printing ink composition 138, the blowing or foamingoperation proceeds selectively as is well known in the chemicalembossing art, and the finished embossed product is illustrated in FIG.11.

The intermediate operations of heating, gelling and firming of theresinous polymer composition 133, the printing of the printing inkcomposition layer 138, the application and the gelling, firming andcooling of the resinous polymer wear layer 122, and the heating, fusion,and blowing or foaming are standard and conventional and have beendescribed previously herein and should requie no further explanation ordescription. It is noted that the mechanical embossing on the surface ofthe wear layer 122 is retained substantially uniformly throughout.

In FIG. 12, there is illustrated a resinous polymer sheet material 140comprising: a typical, relatively flat, backing web or sheet material112; a resinous polymer composition 143 which is potentially foamable ornon-foamable, as desired or required; a substantially uniform resinouspolymer coating such as a clear printing ink composition 144 whichcontains substantially uniformly therein from about 1% to about 35% or40% by weight, and preferably from about 1% to about 10% by weight, of apolymerization initiator, catalyst, or organic peroxide; a printing inkcomposition 148 which does not contain any polymerization initiator,catalyst, or organic peroxide; a relatively thin barrier coat or layer145, if a blowing or foaming agent is included in the resinous polymercomposition layer 143; and a wear layer 142 containing substantiallyuniformly therein one or more reactive polymerizable monomericmaterials.

The standard and conventional operations, such as those of heating,gelling and firming of the resinous polymer plastisol composition 143and of the plastisol wear layer 142, as well as the mechanical embossingof the gelled and cooled surface of the wear layer 142, and thesubsequent heating and fusion, and blowing or foaming of the resinouspolymer composition 143 (if a blowing or foaming agent is includedtherein) follow in well-known fashion.

FIG. 12 illustrates the resinous polymer sheet material 140, eitherimmediately prior to the heating and fusion, and blowing or foamingoperation (if a blowing of foaming agent is present), or subsequent tothe heating and fusion operations, if no blowing or foaming agent waspresent. The mechanical embossing on the entire surface of the wearlayer 142 is retained substantially uniformly throughout theseoperations of heating, fusion, blowing or foaming.

If a blowing or foaming agent had been originally included in theresinous polymer composition 143 of FIG. 12, then such resinous polymercomposition 143 would have become expanded and distended to generallyresemble the blown or foamed resinous polymer composition 123illustrated in FIG. 10.

In a similar way, if a blowing or foaming modifier or inhibitor had beenoriginally included in certain selected, predetermined portions or areasof the printing ink composition 148 of FIG. 12, then such resinouspolymer composition 148 (and all layers thereabove) would have beomeexpanded and distended to generally resemble the blown and chemicallyembossed resinous polymer composition 133 of FIG. 11.

Still another embodiment of the present invention leading to theretention of the overall mechanical embossing on the surface of the wearlayer through the heating and fusion, and blowing or foaming operationsis describable without the need or the necessity for still anotherFigure in the drawings. Such embodiment excludes the presence of anypolymerization initiator, catalyst, or organic peroxide from theprinting ink composition, as in FIGS. 9-11, and also excludes thepresence of any polymerization initiator, catalyst, or organic peroxideexisting in a separate layer, as in FIG. 12.

In this non-illustrated embodiment, the polymerization initiator,catalyst, or organic peroxide is included directly and uniformly in thewear layer containing the reactive polymerizable monomeric materials,usually from about 0.5% by weight to about 5% by weight and preferablyfrom about 1% to about 2% by weight based on the weight of the reactivepolymerizable monomeric materials.

Alternatively, the polymerization initiator, catalyst, or organicperoxide may be included in the barrier coat 115 of FIG. 9 from about0.08% to about 0.8% by weight and preferably from about 0.16% to about0.32% by weight based on the total weight of the barrier coatcomposition.

Activation and polymerization and cross-linking of such reactivepolymerizable monomeric materials takes place during the mechanicalembossing procedure, as usual. Retention of such mechanical embossingeffects is noted at the conclusion of the heating and fusion, andblowing or foaming operations.

The present invention will be described further with particular respectto the following specific examples, wherein there are shown preferredand typical embodiments of the present invention. However, it is to beappreciated that such specific examples are primarily illustrative ofthe general principles of the present invention and that the specificmaterials, chemicals, patterns, designs and other particular aspectsshould not be construed as limitative of the broader scope of thepresent inventive concept, except as defined by the scope and the spiritof the attached claims.

EXAMPLE I

A resinous polymer sheet material such as illustrated in FIGS. 1-3 ofthe drawings is made by the following procedures:

The base layer or substrate comprises a relatively flat, 0.040 inchthick fibrous sheet of felted asbestos fibers with an acrylic smoothleveling coating thereon. The asbestos felt fiber sheet is coatedsubstantially uniformly to a wet thickness of about 0.015 inch with thefollowing potentially foamable resinous polymer plastisol composition:

    ______________________________________                                                                  Parts by                                                                      Weight                                              ______________________________________                                        Polyvinyl chloride, medium mol. wt., general                                  purpose dispersion resin, inh. viscosity 0.99                                                             30.2                                               (ASTMD1243-66)                                                               Polyvinyl chloride, medium mol. wt., dispersion grade                         resin, inherent viscosity 1.0                                                                             8.2                                               Polyvinyl chloride, medium mol. wt., blending resin,                          inherent viscosity 0.9      17.1                                              Anhydrous alumina silicate filler                                                                         6.9                                               Butyl benzyl phthalate      15.4                                              Alkyl benzyl phthalate, low b.p. plasticizer                                                              9.3                                               Polydodecyl benzene         7.4                                               Azodicarbonamide            1.1                                               Accelerator/stabilizer      0.4                                               Titanium dioxide            2.5                                               Dioctyl phthalate           1.5                                               Wetting agent               0.0                                               ______________________________________                                    

Gelling and firming of the potentially foamable plastisol isaccomplished in an oven at an elevated temperature of about 300° F., forabout three minutes. The temperature is not sufficiently elevated as toactivate or decompose the azodicarbonamide.

The gelled potentially foamable plastisol is then printed with a ceramicbrick pattern or design as shown in FIGS. 2 and 3 of the drawings. ZonesB are printed with a standard or conventional printing ink compositioncontaining a predetermined pigment but which does not contain any blowmodifier or inhibitor or any free-radical polymerization initiator ororganic peroxide. Such a standard or conventional printing inkcomposition comprises:

    ______________________________________                                                                    Parts                                             ______________________________________                                        Solution grade copolymer of vinyl chloride (90 parts) and                     vinyl acetate (10 parts)      15                                              Methyl ethyl ketone           85                                              Pigment or coloring agent, as desired or required                             ______________________________________                                    

Zones A, however, are printed with the following printing inkcomposition containing a different pigment or coloring agent:

    ______________________________________                                                                    Parts                                             ______________________________________                                        Solution grade copolymer of vinyl chloride (90 parts) and                                                   12                                              vinyl acetate (10 Parts)                                                      Methyl ethyl ketone           66                                              Dicumyl peroxide               2                                              Trimellitic anhydride         20                                              Pigment or coloring agent, as desired or required                             ______________________________________                                    

The printed, gelled potentially foamable plastisol is then allowed todry and a wear layer is applied thereto to a wet thickness of about0.015 inch and having the following formulation:

    ______________________________________                                                                    Parts                                             ______________________________________                                        Polyvinyl chloride, dispersion grade, inherent viscosity                      0.8                           100                                             Trimethylolpropane trimethacrylate (90 ppm hydroquinone)                                                     25                                             Butyl benzyl phthalate plasticizer                                                                          13.8                                            2,4,4-trimethyl pentyl-3,5-diisobutyrate                                                                    3.3                                             Alkyl benzyl phthalate low boiling point plasticizer                                                        4.1                                             Ba-Zn phosphite heat stabilizer                                                                             6.4                                             Epoxidized tall oil           2.4                                             ______________________________________                                    

Gelling and firming of the wear layer plastisol is accomplished byheating in an oven atmosphere having an elevated temperature of justunder 300° F., for a period of time of about 3 minutes.

The gelled wear layer is then mechanically embossed with a fine overallpattern of a parchment paper-like texture in a Watson-Stillman Press forabout 2 minutes under a pressure of about 140 psig and at an elevatedtemperature created in the wear layer of just over 300° F. The heatedembossing takes place, along with the polymerization and/orcross-linking of the trimethylolpropane trimethacrylate in the wearlayer but only in those portions thereof lying directly over the dicumylperoxide, whereas there is substantially no polymerization and/orcross-linking to any significant or substantial degree in those otherareas of the wear layer not lying directly over the dicumyl peroxide.Additionally, the melt viscosity of the wear layer portions lying overthe dicumyl peroxide is materially increased, whereas the melt viscosityof the wear layer portions not lying over the dicumyl peroxide issubstantially unchanged.

The mechanically embossed material is then heated in a fusion ovenmaintained at an elevated temperature of about 395° F., for about 23/4minutes. Fusion of the resins takes place, along with the blowing andfoaming of the potentially foamable plastisol in those areas not lyingdirectly under the trimellitic anhydride inhibitor in the printing inkcomposition. There is very little blowing or foaming in the areas lyingdirectly under the trimellitic anhydride. The chemical embossingdifferential effect is excellent.

In addition, the elevated portions or lands of the wear layer, as seenin FIG. 3 of the drawings, develop a sleek, glossy or lustrous finish ortexture, with high brilliance and sheen, whereas the lower or depressedportions or mortars retain the flat, dead or dull mat finish createdtherein by the mechanical embossing in the Watson-Stillman Press. Theappearance of the material, after the blowing or foaming cycle is verymuch like that of a glossy, glazed ceramic tile of high sheen,surrounded by a flat, dead or dull mat finish giving the appearance ofgrout or other cementitious material between the ceramic tiles.

The different colors of the printed pattern or design of the printingink composition are in complete and perfect registry with (1) theabove-described mechanical embossing effects of the contrasting sleek,glossy or lustrous areas and the flat, dead or dull areas, as well as(2) the above-described chemical embossing effect of higher and lowerareas on the surface of the wear layer.

Testing by means of solubility in tetrahydrofuran establishes that thetrimethylolpropane trimethacrylate is not polymerized or cross-linkedprior to the mechanical embossing; that it is polymerized andcross-linked during the mechanical embossing; and that it is stillpolymerized and cross-linked after the blowing and foaming cycle iscomplete but only in those areas of the wear layer lying directly overthe dicumyl peroxide present in the printing ink composition, whereasall other areas of the wear layer not lying directly over the dicumylperoxide, there is substantially no polymerization or cross-linking ofthe trimethylolpropane trimethacrylate.

With further reference to the melt viscosity determinations for therelatively highly polymerized and cross-linked portions and therelatively lowly polymerized and un-cross-linked portions of theresinous wear layer, it has been established that the following meltviscosity ranges are suitable for the application of the principles ofthe present inventive concept.

Using the conditions set forth in Example I for the Brabenderdeterminations, the torque readings for the highly cross-linked portionsof the wear layer should be in the range of from about 1000 to about4000 meter-grams and the torque readings for the relativelyun-cross-linked portions should be in the range of from about 300 toabout 900, with differences in the torque readings for the twocontrasting portions in the same product being at least about 250 metergrams.

It is to be appreciated that the references in the preceding paragraphand elsewhere in this disclosure to cross-linked polymeric materialsrefers solely to the polymerization and cross-linking of thepoly-functional reactive polymerizable monomeric materials, such as thetrimethylolpropane trimethacrylate, for example, in the resinous wearlayer, which, of course, is cross-linked and thermoset.

It is also to be appreciated that the main resin in the wear layer, thepolyvinyl chloride, for example, is substantially uniformly andhomogeneously distributed therein and is in a fused and polymerizedstate. However, it is not cross-linked and is still in a thermo-plasticstate, as compared to the cross-linked and thermoset polyfunctionalpolymeric materials in those portions of the wear layer lying over thepolymerization or cross-linking initiator or organic peroxide.

It is also to be observed that there is complete and perfect registrybetween: the flat, dead or dull textured portions of the wear layer;their corresponding colored portion of the pattern or design of theprinting ink composition; and the relatively unblown or unfoamedportions of the resinous polymer composition 16. At the same time, thereis complete and perfect registry between: the sleek, glossy or lustrousfinish surfaces; their corresponding colored portions of the pattern ordesign of the printing ink composition; and the blown and foamedportions of the resinous polymer composition.

With respect to the determination of the melt viscosities of the variousportions of the resinous wear layer, such is a relatively morecomplicated procedure. Resort to the C. W. Brabender Plastograph, or"Plasticorder," as described in Paint and Varnish Production, July,1965, however, makes such determinations relatively simple and veryaccurate. Additional information on such procedures is also to be foundon pages 23 through 32 of the Journal of Cellular Plastics,January/February, 1971. Brabender determinations are run on samples ofthe highly polymerized portions of the resinous wear layer and on therelatively unpolymerized portions of the resinous wear layer at 150° C.,at a shear rate of 30 revolutions per minute for fifteen minutes atwhich time the 53-gram samples are at equilibrium. A type 6 roller mixermeasuring head is used to determine the melt rheology of the wear layerplastisols. The highly polymerized portions of the resinous wear layeryield torque readings of 2510 meter grams, whereas the relativelyunpolymerized portions yield readings of only 650 meter grams.

EXAMPLE II

A resinous polymer sheet material such as is illustrated in FIG. 7 ofthe drawings is made as follows:

The procedures described in Example I are followed substantially as setforth therein with the exception that the trimellitic anhydride isomitted from the printing ink composition which comprises the followingingredients:

    ______________________________________                                                                    Parts                                             ______________________________________                                        Solution grade copolymer of vinyl chloride (90 parts) and                                                   15                                              vinyl acetate (10 parts)                                                      Methyl ethyl ketone           83                                              Dicumyl peroxide               2                                              Trimellitic anhydride          0                                              Pigment or coloring agent, as desired or required                             ______________________________________                                    

The results obtained in this Example are generally comparable to theresults obtained in Example I, with the exception that the resinouspolymer sheet material of this Example is not chemically embossed andthe blowing or foaming operation is substantially uniform in its effectwhereby the surfaces of the wear layer are substantially level and ofthe same height. The flat, dead or dull embossed mat finish and thesleek, glossy or lustrous finish lie substantially in the same levelplane. With respect to the concentration of polymerized or cross-linkedtrimethylolpropane trimethacrylate, it is relatively high in those areaslying over the dicumyl peroxide and relatively low in those areas notlying directly over the dicumyl peroxide. The melt viscosities are againrelatively higher and lower, as indicated in Example I. Bumps as shownin the drawings are discernible and felt by the "finger-test." Barriercoat BC-1 is used in order to insure that no gases developed during theblowing or foaming escape up into the wear layer.

EXAMPLE III

A resinous polymer sheet material such as is illustrated in FIG. 8 ofthe drawings is made as follows:

The procedures described in Example II are followed substantially as setforth therein with the exception that, in addition to the omission ofthe trimellitic anhydride blow modifier or inhibitor from the printingink composition, the azodicarbonamide blowing or foaming agent isomitted from the plastisol formulation.

The results obtained in this Example are generally comparable to theresults obtained in Example II, with the exception that the resinouspolymer composition or plastisol is not chemically blown or foamed atall and the result is a more dense, non-cellular polymer sheet materialin which the fused resins are heavier and are not too much unlike thatportion of the fused resins illustrated in FIG. 3 of the drawings, lyingunder the portions of the printing ink composition containing the blowmodifier or inhibitor. Such portions are identified in FIG. 1 by thereference letter A. In the product of FIG. 8, substantially all portionsof the fused plastisol are similar.

Again, the flat, dead or dull mat texture of zones A is retained afterthe mechanical embossment and through the fusion heating at elevatedtemperatures. However, such texture in zones B is lost during the fusionheating at the elevated temperatures and the final appearance of suchzones B is sleek, glossy and lustrous. Elevated or raised bumps shown inthe drawings are detectible and felt by the "finger-test". Inasmuch asno blowing or foaming is involved in this Example, no barrier coat isemployed.

EXAMPLE IV

The procedures described in Example I are followed substantially asdescribed therein, with the exception that the proportions of theconstituents of the printing ink composition which contained both thefree-radical polymerization or organic peroxide and the blow modifier orinhibitor are changed as follows:

    ______________________________________                                                                    Parts                                             ______________________________________                                        Pigmented reducing clear (solution grade copolymer of                         90 parts vinyl chloride and 10 parts vinyl acetate in methyl                  ethyl ketone, plus pigment)   70                                              Trimellitic anhydride chemical inhibitor                                                                    20                                              40% dicumyl peroxide (active), supported on precipitated                      calcium carbonate             10                                              ______________________________________                                    

The results of this Example are generally comparable to the results ofExample I.

Again, it is determined that the polyfunctional reactive polymerizablemonomeric material, namely, the trimethylolpropane trimethacrylate, ispolymerized and is cross-linked solely in those areas of the wear layerlying directly over the polymerization initiator, namely, the dicumylperoxide. In those other portions of the wear layer not lying directlyover the dicumyl peroxide, the trimethylolpropane trimethacrylate issubstantially unpolymerized and is not cross-linked.

EXAMPLE V

The procedures generally described in Example I are followedsubstantially as set forth therein with certain variations as follows:the P-1 potentially foamable plastisol composition is used; the wetthickness is about 18.7 mils; gelling takes place in a heated airatmosphere at about 300° F., for 3 minutes; a BC-1 barrier coat is usedand has a thickness of about 3 mils; it is gelled in a heated airatmosphere at about 300° F., for about 3 minutes; the printing inkcomposition is P-1 and contains dicumyl peroxide and trimelliticanhydride as the polymerization initiator or organic peroxide and theblow modifier or inhibitor respectively; the non-active printing inkcomposition contains no polymerization initiator or organic peroxide orany equivalent material; the resinous wear layer is a W-1 compositionand contains trimethylolpropane trimethacrylate as the reactivepolymerizable monomer; it is about 12 mils thick and is gelled in aheated air atmosphere at about 300° F., for about 3 minutes; mechanicalembossing takes place at about 305° F., under an applied pressure of 110psig for 3 minutes against a coarsely textured parchment type releasepaper; blowing and foaming take place in a heated fusion oven at anelevated temperature of about 395° F., for about 2 minutes and fortyseconds.

The results obtained in this Example are generally comparable to theresults obtained in Example I. The relatively low, relatively unblownmortar areas have embossed, flat, dead or dull finishes or textures,whereas the relatively elevated, relatively blown land areas possess asleek, glossy or lustrous surface. The mortar areas have a relativelyhigh concentration of polymerized cross-linked monomer and have a highmelt viscosity. The land areas have practically no concentrations ofpolymerized cross-linked monomer and have a relatively low meltviscosity. The product is commercially acceptable as a resilient floorcovering.

EXAMPLES VI-XVI

The procedures set forth in Example V are followed substantially asdescribed therein with the exception that the P-1 printing inkcomposition used therein is replaced by printing ink compositions P-7through P-17, as described previously herein, as eleven additionalExamples:

The results of these Examples are generally comparable to the resultsobtained in Example V. The relative differences between (1) the flat,dead or dull mat textured finishes and the sleek, glossy or lustrousareas and (2) the degree of polymerization and/or cross-linking of thereactive polymerizable monomer in these areas and (3) the degree ofincrease in the melt viscosity of the polymerized and cross-linked areasis significant and notable.

EXAMPLES XVII-XXI

The procedures described in Example V are followed substantially asdescribed therein with the exception that the dicumyl peroxidepolymerization initiator in the printing ink composition is replaced by:

Example XVII--t-butyl peroxyacetate

Example XVIII--2,5-dimethyl-2,5-bis(benzoylperoxy)hexane

Example XIX--t-butyl peroxyneodecanoate

Example XX--t-butyl peroxy maleic acid

Example XXI--2,5-dimethyl-2,5-bis(2-ethylhexylperoxy)hexane

The results of these Examples are generally comparable to the resultsobtained in Example V.

EXAMPLES XXI-XXV

The procedures set forth in Example V are followed substantially asdescribed therein with the following exceptions, with respect to theprinting ink compositions used therein, wherein printing inkcompositions identified as P-2 through P-5 in the pertinent table areused:

Example XXII (P-2) contains trimellitic anhydride but no dicumylperoxide or any other polymerization initiator or organic peroxide. Thisyields a product structurally shown in FIGS. 2 and 3 of the drawings butwithout any embossed, flat, dead or dull textured areas, and with noportions having increased melt viscosities.

Example XXIII (P-3) contains trimellitic anhydride and dicumyl peroxide.This yields a product generally comparable to the product obtained inExample V. It possesses embossed, flat, dead or dull textured areas andsleek, glossy or lustrous finish areas and differentials in meltviscosities. It is commercially acceptable as a resilient floorcovering.

Example XXIV (P-4) contains trimellitic anhydride but no dicumylperoxide or any other polymerization initiator or organic peroxide. Thisyields a product structurally shown in FIGS. 2 and 3 of the drawings butwithout any embossed, flat, dead or dull textured areas and with noportions having increased melt viscosities.

Example XXV (P-5) contains dicumyl peroxide but no trimellitic anhydrideor any other blow modifier or inhibitor. This yields a productstructurally similar to that shown in FIG. 7 of the drawings. There areembossed, flat, dead or dull textured areas, as well as sleek, glossy orlustrous finish areas, and differentials in melt viscosities, but thereis no chemical embossment in the surface of the wear layer, other thanthe small elevated or raised bumps shown in FIG. 7.

EXAMPLES XXVI-XXXI

The procedures described in Example V are followed substantially as setforth therein with the exception that the wear layer composition W-1used therein is replaced by wear layer compositions W-3, W-6, W-7, W-9,W-10 and W-12, as described in the pertinent table herein. The resultsof these Examples are generally comparable to the results obtained inExample V with wear layer composition W-1. The contrast between theembossed, flat, dead or dull textured areas and the sleek, glossy orlustrous smooth finish areas is very pronounced. The differences inpolymerization and/or cross-linking of the reactive polymerizablemonomers in the respective wear layers are marked and considerable. Thedifferences in the melt viscosities of the various areas of the wearlayer is also observed and is marked and considerable. The products arecommercially acceptable as resilient floor coverings.

EXAMPLES XXXII-XXXVI

The procedures described in Example V are followed substantially as setforth therein with the exception that the trimethylolpropanetrimethacrylate reactive polymerizable monomer is replaced by:

Example XXXII--Triethylene glycoldiacrylate

Example XXXIII--Tetraethylene glycol diacrylate

Example XXXIV--1,6-hexanediol diacrylate

Example XXXV--Neopentyl glycol dimethacrylate

Example XXXVI--Trimethylolpropane triacrylate

The results of these Examples are generally comparable to the resultsobtained in Example V. The polymerization and/or cross-linking and theincrease in melt viscosity are as described therein, along with thecontrasting flat, dead or dull textures areas and the sleek, glossy orlustrous areas.

EXAMPLE XXXVII

The procedures set forth in Example I are followed substantially asdescribed therein with the exception that the composition of theresinous wear layer is changed to the following:

    ______________________________________                                        (Parts by weight, based on 100 parts of resin, phr)                                                       Parts                                             ______________________________________                                        Polyvinyl chloride, dispersion grade, inherent viscosity                      0.8                           50                                              Polyvinyl chloride, blending resin, inherent viscosity 0.71                                                 50                                              Trimethylolpropane trimethacrylate (90 ppm hydroquinone)                                                    25                                              Butyl benzyl phthalate        13.8                                            2,4,4-trimethyl pentyl-3,5-diisobutyrate                                                                    3.3                                             Alkyl benzyl phthalate        4.1                                             Ba-Zn phosphite heat stabilizer                                                                             6.4                                             Epoxidized tall oil           2.4                                             ______________________________________                                    

The results of this Example are generally comparable to the resultsobtained in Example I. The differences in polymerization and/orcross-linking of the reactive polymerizable monomer and the differencein melt viscosities of the various portions of the wear layer are noted,along with the contrasting surfaces of a flat, dead or dull mat textureand a sleek, smooth, glossy or lustrous finish. The product iscommercially acceptable as a resilient floor covering. Similar to theproduct of Example I, the portion of the wear layer in the flat, dead ordull mat finish area is cross-linked and thermoset, whereas the portionof the wear layer in the sleek, smooth, glossy or lustrous finish areasis not cross-linked nor is it thermoset but is still thermoplastic.

EXAMPLE XXXVIII

The procedures described in Example V are followed substantially asdescribed therein with the exception that the barrier coat compositionBC-1 which is used therein is replaced by the barrier coat compositionBC-2, as previously described hereinbefore. The results of this Exampleare generally comparable to the results obtained in Example V. Thethickness of the barrier coat is also 4.5 mils.

EXAMPLES XXXIX-XLI

The procedures described in Example V are followed substantially asdescribed therein with the exception that the thickness of the barriercoat is changed to 1.5 mils, 4 mils, and 5 mils, rather than the 4.5mils thickness it possessed in Example V. The results of these Examplesare generally comparable to the results obtained in Example V.

EXAMPLES XLII-XLIV

The procedures described in Example V are followed substantially as setforth therein with the exception that the mechanical embossing takesplace under applied pressures of 50 psig, 86 psig and 100 psig, ratherthan the applied pressure of 110 psig as employed in Example V. Theresults of these Examples are generally comparable to the resultsobtained in Example V. The flat, dead or dull mat finish areas containcross-linked and thermoset resin, whereas the sleek, smooth, glossy orlustrous finish areas contain un-cross-linked, thermoplastic resin.

EXAMPLE XLV

The procedures described in Example V are followed substantially as setforth therein with the exception that the conditions for the mechanicalembossing of the resinous wear layer are changed to: 140 psig, at 360°F., for a period of time of about 15 seconds.

The results of this Example are generally comparable to the resultsobtained in Example V.

EXAMPLE XLVI

The procedures described in Example V are followed substantially as setforth therein with the exception that the conditions for the mechanicalembossing of the resinous wear layer are changed to: 86 psig, 315° F.,for a period of time of about 2 minutes.

The results of this Example are generally comparable to the resultsobtained in Example V.

EXAMPLE XLVII

The procedures described in Example I are followed substantially asdescribed therein with the exception that the mechanical embossing ischanged as follows:

Instead of applying pressure and heat to the coarsely textured,parchment-type release paper placed on the surface of the gelledresinous wear layer by means of a Watson-Stillman Press platen, thepressure and heat are applied by rolling contact with a 24-in. rotatingembossing roll having a temperature of about 330° F., and rotating at aspeed of 2 revolutions per minute. The surface of the embossing roll hasa roughened, sand-blasted finish. The resinous wear layer is guidedagainst the heated periphery of the embossing roll and is held in tightcontact therewith for the major portion of the heated periphery, afterpassing through the pressure-applying roll-nip, thus creating about a5-foot useful heated contacting periphery.

The results of this Example are generally comparable to the resultsobtained in Example I. The polymerized and cross-linked thermosetportions of the resinous wear layer which have the higher melt viscosityretain the surface features and characteristics of the coarsely-texturedparchment-type release paper, whereas the un-cross-linked thermoplasticportions of the resinous wear layer becomes sleek, smooth and glossy andlustrous.

EXAMPLE XLVIII

The procedures described in Example XLVII are followed substantially asset forth therein with the exception that the heated, pressure-applyingembossing roll is engraved with very fine parallel lines, fifty lines tothe inch, which create the flat, dead or dull mat texture or finish, andcontain cross-linked, thermoset resin, in contrast to the sleek, smooth,glossy or lustrous portions which contain un-cross-linked thermoplasticresin. The results of this Example are generally comparable to theresults of Example XLVII.

EXAMPLE XLIX

The resinous polymer sheet material illustrated in FIGS. 2 and 3generally is made by the following alternative "upside-down" procedurewherein the composition of the potentially foamable plastisol, theprinting ink compositions, the barrier coat composition, and the wearlayer composition are as described in Example V.

The resinous wear layer plastisol containing the reactive polymerizablemonomer and while still in highly fluid form is cast upon the surface ofa coarsely textured, parchment-type release paper to a depth of about 15mils. The wear layer plastisol is sufficiently fluid as to flow into andcompletely fill all the irregular recesses of the release paper, therebyassuming the surface features and characteristics of the release paper.The wear layer is then gelled at 300° F.

The various printing ink compositions, some containing both dicumylperoxide polymerization initiator and trimellitic anhydride blowmodifier and others not containing any polymerization initiators ororganic peroxides or any blow modifiers or inhibitors, are applied tovarious areas of the exposed face of the gelled wear layer in thedesired pattern or design. The printing ink compositions are then dried.

A 3-mil barrier coat is applied and adhered to the printing inkcompositions and is heated at a temperature of about 320° F., for asufficient period of time to not only gel the resinous barrier coat butalso to activate or decompose the dicumyl peroxide in the wear layer topolymerize and/or cross-link the reactive polymerizable monomers lyingin the same vertical zones and to increase the melt viscosities of theresins in such vertical zones.

A base layer or substrate comprising a potentially foamable plastisolcomposition and an adhered fibrous sheet of felted asbestos fibers isthen laminated to the gelled barrier coat by passage through a laminatordevice under pressure and at an elevated temperature. The resultinglaminated product is unitary and integral in structure.

The coarsely textured parchment-type release paper is then stripped'from the wear layer whose surface is thus exposed and found to becorespondingly coarsely textured and parchment-like in appearance,possessing a flat, dead or dull texture all over its surface.

This laminated product is then passed through a heated fusion oven attemperatures of about 395° F., and the resins are fused along with theblowing and the foaming operation wherein the blowing and foaming agentand the blowing modifier or inhibitor carry out their previouslydescribed chemical embossing procedures.

The resulting blown product is generally similar and comparable to theproduct of Example V. Those portions of the wear layer wherein thereactive polymerizable monomers are polymerized and/or cross-linked andalso possess a higher melt viscosity retain their coarsely texturedparchment-type, flat, dead or dull mat structure and appearance. Inother portions of the wear layer wherein there was substantially nopolymerization and/or cross-linking of the reactive polymerizablemonomers and wherein the melt viscosity is still relatively unchangedand is relatively low, the surfaces are melted to form sleek, smooth,glossy or lustrous finishes, occurring during the blowing and thefoaming operation. The cross-linked portions are thermoset, whereas theportions which are not cross-linked are thermoplastic.

EXAMPLE I

The procedures described in Example V are followed substantially as setforth therein with the exception that cumene hydroperoxide which is apolymerization initiator or organic peroxide activatable or decomposableonly at relatively high temperatures is additionally included in theresinous wear layer substantially uniformly in a concentration of about7 parts by weight based on 100 parts of resin, phr.

The cumene hydroperoxide is not activated or decomposed during thegelling operations or during the mechanical embossing operations, atwhich time the dicumyl peroxide is activated or decomposed in theprinting ink composition whereby certain selected portions of the wearlayer become polymerized and/or cross-linked, and develop relativelyhigh melt viscosities, as described in this specification and in ExampleV in greater detail.

However, the cumene hydroperoxide is subsequently activated ordecomposed at the more elevated temperatures which are present duringthe fusion, blowing or foaming cycle, whereby the reactive polymerizablemonomers in the remaining sleek, smooth, glossy or lustrous finish areasare polymerized and/or cross-linked at that time, along with theincrease in the melt viscosities in such sleek, smooth, glossy orlustrous portions. Apparently, the softening, melting and flowing insuch areas precedes the polymerization and/or cross-linking and increasein melt viscosities in such areas.

There is no substantial change in the flat, dead or dull textured areaswhich are polymerized and/or cross-linked and have relatively high meltviscosities. Thus, the entire surface is polymerized and/or cross-linkedand have relatively high viscosities.

EXAMPLE LI

Gloss level measurements are obtained for the wear layer surfaces (bothland and mortar areas) of various polyvinyl chloride resinous sheetmaterials which are made by hand-operated, manually controlledlaboratory procedures at 60°, using a Gardner Laboratories glossmeterstandardized to an appropriate gloss plate for the 60° meter. Suchlaboratory procedures are not as sophisticated or as refined as arecommercial plant manufacturing procedures and occasional blisters andirregularities cause lower than normal gloss readings. The variouspolyvinyl chloride resinous sheet materials are obtained by theprocedures generally described in Example I, with any variations in suchprocedures being noted.

    ______________________________________                                                                         Mea-                                                                          sure-                                                                 Gloss   ments                                        Variations from Example I                                                                              Land    Mortar                                       ______________________________________                                        No variations from Example I                                                                           16      4                                            Inhibitor is 25% trimellitic anhydride                                                                 28      8                                            Inhibitor is 25% trimellitic anhydride                                                                 25      4                                            Inhibitor is 25% trimellitic anhydride                                                                 33      6                                            Monomer is 28 phr 1,6-hexanediol dimethacrylate                                                        44      11                                           Monomer is 28 phr 1,6-hexanediol dimethacrylate                                                        29      7                                            Monomer is 20 phr pentaerythritol triacrylate                                                          20      7                                            Monomer is 20 phr pentaerythritol triacrylate                                                          37      13                                           Inhibitor is 20% Benzotriazole; dicumyl peroxide                              is increased to 10%      15      4                                            No peroxide included (Control)                                                                         20      19                                           No peroxide included (Control)                                                                         22      18                                           ______________________________________                                    

EXAMPLE LII

Gloss level measurements are obtained for the wear layer surfaces (bothland and mortar) of various polyvinyl chloride resinous sheet materialswhich are made by automated, electronically-controlled commercialproduction plant procedures, at 60° using a Gardner Laboratoriesglossmeter standardized to an appropriate gloss plate for the 60° meter.Such commercial production plant procedures are very sophisticated andvery refined and yield gloss level measurements higher than thoseobtained by laboratory procedures. The various polyvinyl chlorideresinous sheet materials are obtained by the procedures generallydescribed in Example I, with any variations in such procedures beingnoted.

    ______________________________________                                                                         Mea-                                                                          sure-                                                                 Gloss   ments                                        Variations from Example I                                                                              Land    Mortar                                       ______________________________________                                        No variations from Example I                                                                           72      20                                           Inhibitor is 25% trimellitic anhydride                                                                 78      19                                           Inhibitor is 25% trimellitic anhydride                                                                 79      18                                           Inhibitor is 25% trimellitic anhydride                                                                 72      17                                           Monomer is 28 phr 1,6-hexanediol                                                                       80      27                                           dimethacrylate                                                                Monomer is 28 phr 1,6-hexanediol                                                                       71      21                                           dimethacrylate                                                                Monomer is 20 phr pentaerythritol triacrylate                                                          67      16                                           Monomer is 20 phr pentaerythritol triacrylate                                                          72      20                                           Inhibitor is 20% Benzotriazole; dicumyl peroxide                              is increased to 10%      63      14                                           ______________________________________                                    

EXAMPLE LIII

Hot melt viscosities for various polyvinyl chloride plastisols areobtained, employing the C. W. Brabender "Plasticorder" with a jackettemperature of 150° C.--to equilibrium in fifteen minutes; a shear rateof thirty revolutions per minute; and a sample weight of 53 grams.

In the following charts, the reactive polymerizable monomeric materialsand the organic peroxide or free-radical polymerization initiator are asindicated. Monomer "A" is trimethylolpropane trimethacrylate; monomer"B" is 1,6-hexanediol dimethacrylate; and monomer "C" is pentaerythritoltriacrylate. The organic peroxide or free-radical polymerizationinitiator is 40% active dicumyl peroxide, supported on precipitatedcalcium carbonate. The resin for the first two controls is 100 partsFirestone polyvinyl chloride resin 605. The resin for the second twocontrols is 89.5 parts of Geon polyvinyl chloride resin 120×271 and 10.5parts of Tenneco 501. The resin for the second chart is 100 partsFirestone polyvinyl chloride resin 605. 53.3 parts per hundred resinplasticizer blend are used for the controls.

    ______________________________________                                                           Hot Melt Viscosity                                         Controls           Meter-grams                                                ______________________________________                                        No Monomer         600                                                        No Monomer         600                                                        No Monomer         840                                                        No Monomer         820                                                        ______________________________________                                    

    ______________________________________                                              Plasti-        Mono- Mono- Mono-                                              cizer   Per-   mer   mer   mer    Hot Melt                                    Blend   oxide  "A"   "B"   "C"    Viscosity                             Resin phr     phr    phr   phr   phr    Meter Grams                           ______________________________________                                        100   23.3    1.59   30                 3180                                  100   23.3    1.59   30                 3210                                  100   23.2    7.95   30                 3210                                  100   23.2    7.95   30                 3130                                  100   38.3    1.59   15                 1510                                  100   38.3    1.59   15                 1470                                  100   38.3    7.95   15                 1250                                  100   38.3    7.95   15                 1250                                  100   25.3    1.59         28           2160                                  100   25.3    1.59         28           2100                                  100   25.3    7.95         28           2070                                  100   25.3    7.95         28           2050                                  100   39.3    1.59         14           1120                                  100   39.3    1.59         14           1090                                  100   39.3    7.95         14           1150                                  100   39.3    7.95         14           1150                                  100   23.3    1.59               30     3430                                  100   23.3    1.59               30     3400                                  100   23.3    7.95               30     3210                                  100   23.3    7.95               30     3380                                  100   38.3    1.59               15     1460                                  100   38.3    1.59               15     1440                                  100   38.3    7.95               15     1470                                  100   38.3    7.95               15     1460                                  ______________________________________                                    

EXAMPLE LIV

The procedures set forth in Example I are followed substantially asdescribed therein with the exceptions that a barrier coat or layer isused, as shown in FIG. 9, and all the various colored portions and areasof the printing ink composition used in applying the desired pattern ordesign to the gelled and cooled resinous polymer plastisol compositionhave the following formulations containing the same concentrations andamounts of dicumyl peroxide polymerization initiator or catalyst:

    ______________________________________                                                                    Parts                                             ______________________________________                                        Solution grade copolymer of vinyl chloride (90 parts)                         and vinyl acetate (10 Parts)  15                                              Methyl ethyl ketone           83                                              Dicumyl peroxide               2                                              Pigments or colorants, as desired or required,                                in the particular pattern or design                                           ______________________________________                                    

The product, immediately prior to the heating and fusion, and blowing orfoaming operation, is illustrated in FIG. 9.

Omisssion of the azodicarbonamide blowing or foaming agent (1.1 parts)from the formulation of the resinous polymer plastisol composition ofExample I provides a final unblown or unfoamed product, such asillustrated in FIG. 9, wherein the mechanical embossing is substantiallycompletely retained throughout the heating and fusion, and blowing orfoaming operations. In such a case where there is no blowing or foaming,the barrier coat or layer is eliminated.

Inclusion of the azodicarbonamide blowing or foaming agent (1.1 parts)in the formulation of the resinous polymer plastisol composition ofExample I provides for a blown final product, such as illustrated inFIG. 10, wherein the mechanical embossing is substantially completelyretained throughout the heating and fusion, and blowing or foamingoperations. In such a case, a barrier coat or layer may be used.

Substitution of certain selected printing ink compositions havingformulations as shown above in this Example which contain no blowing orfoaming modifiers or inhibitors therein by other selected printing inkcompositions having formulations as shown hereinafter in this Examplewhich contain trimellitic anhydride blowing or foaming modifier orinhibitor provides for surface embossed effects in the blown or foamedfinal product.

    ______________________________________                                                                    Parts                                             ______________________________________                                        Solution grade copolymer of vinyl chloride (90 parts)                         and vinyl acetate (10 parts)  12                                              Methyl ethyl ketone           66                                              Dicumyl peroxide               2                                              Trimellitic anhydride         20                                              Pigments or colorants, as desired or required,                                in the particular pattern or design                                           ______________________________________                                    

The final blown or foamed, chemically surface embossed product isillustrated in FIG. 11. The mechanical embossing on the surface of thewear layer is substantially completely retained throughout the heatingand fusion, and blowing or foaming operations in this latter form of theExample, as well as in all other forms of this Example.

EXAMPLE LV

The procedures set forth in Example I are followed substantially asdescribed therein, with the exception that none of the printing inkcompositions contain any polymerization initiators, catalysts, ororganic peroxides and have the following formulations:

    ______________________________________                                                                    Parts                                             ______________________________________                                        Solution grade copolymer of vinyl chloride (90 parts)                         and vinyl acetate (10 parts)  15                                              Methyl ethyl ketone           85                                              Pigments or colorants, as desired or required                                 by the particular pattern or design                                           ______________________________________                                    

However, a separate layer or coating such as a clear printing inkcomposition containing dicumyl peroxide polymerization initiator orcatalyst is applied overall, as shown in the structure of the productillustrated in FIG. 12. Such a clear printing ink composition has thefollowing formulation:

    ______________________________________                                                                    Parts                                             ______________________________________                                        Solution grade copolymer of vinyl chloride (90 parts)                         and vinyl acetate (10 parts)  15                                              Methyl ethyl ketone           83                                              Dicumyl peroxide               2                                              ______________________________________                                    

The structure of the product, immediately prior to the heating andfusion, and blowing or foaming operations is illustrated in FIG. 12. Thestructure of the product, subsequent to any heating and fusion, andblowing or foaming, is not illustrated but the mechanical embossing issubstantially completely retained on the surface of the wear layerthrough the heating and fusion, and blowing or foaming operations asshown in other Figures of the drawings.

EXAMPLE LVI

The procedures set forth in Example I are followed substantially asdescribed therein with the exceptions that a barrier coat or layer isused and none of the printing ink compositions have any polymerizationinitiators, catalysts, or organic peroxides therein. Such printing inkcompositions have the following formulations:

    ______________________________________                                                                    Parts                                             ______________________________________                                        Solution grade copolymer of vinyl chloride (90 parts)                         and vinyl acetate (10 parts)  15                                              Methyl ethyl ketone           85                                              Pigments or colorants, as desired or required                                 by the particular pattern or design                                           ______________________________________                                    

In addition, no separate overall layer or coating such as a clearprinting ink composition containing any polymerization initiators,catalysts, or organic peroxides as is used in Example LV, is included inthe structure of the product.

Such polymerization initiator, catalyst, or organic peroxide however isincluded directly and uniformly in the wear layer which possess thefollowing formulation:

    ______________________________________                                                                   Parts                                              ______________________________________                                        Polyvinyl chloride, dispersion grade, inherent                                viscosity 0.8                100                                              Trimethylolpropane trimethacrylate (90 ppm                                    hydroquinone)                25                                               Butyl benzyl phthalate plasticizer                                                                         13.8                                             2,4,4-trimethyl pentyl-3, 5-diisobutyrate                                                                  3.3                                              Alkyl benzyl phthalate low boiling point plasticizer                                                       4.1                                              Ba-Zn phosphite heat stabilizer                                                                            6.4                                              Epoxidized tall oil          2.4                                              Dicumyl peroxide polymerization initiator                                                                  0.3                                              ______________________________________                                    

The product, immediately prior to the heating and fusion, and theblowing or foaming operation, is generally similar to the product whichis illustrated in FIG. 1 of the drawings. Subsequently, it is observedthat the mechanical embossing on the surface of the wear layer issubstantially retained completely through the heating and fusion, andthe blowing or foaming operation.

EXAMPLE LVII

The procedures set forth in Example I are followed substantially asdescribed therein with the exceptions that a barrier coat or layer isused and none of the printing ink compositions have any polymerizationinitiators, catalysts, or organic peroxides therein. Such printing inkcompositions have the formulations described in Example LVI.

In addition, no separate overall coating such as a clear printing inkcomposition containing any polymerization initiators, catalysts, ororganic peroxides, as is used in Example LV is included in the structureof the product.

Such polymerization initiator, catalyst, or organic peroxide, however isincluded directly and uniformly in the barrier coat which possesses thefollowing formulation:

    ______________________________________                                                                    Parts                                             ______________________________________                                        Polyvinyl chloride, high molecular weight,                                    dispersion grade, inherent viscosity 1.4                                                                    89                                              Polyvinyl chloride, high molecular weight,                                    blending resin, inherent viscosity 0.9                                                                      11                                              Epoxidized soya oil           5                                               2,2,4-trimethyl 1-1,3-pentanediol diisobutyrate                                                             6.9                                             Butyl benzyl phthalate        29                                              Polydodecyl benzene           8.5                                             Ba-Zn phosphite stabilizer    7.25                                            UV absorber                   0.32                                            Toner                         0.01                                            Dicumyl Peroxide polymerization initiator                                                                   0.5                                             ______________________________________                                    

The product, immediately prior to the heating and fusion, and theblowing or foaming operation, is generally similar to the product whichis illustrated in FIG. 9 of the drawings except that the printing inkcompositions contain no polymerization initiators, catalysts or organicperoxides. Subsequently, it is observed that the mechanical embossing onthe surface of the wear layer is substantially retained completelythrough the heating and fusion, and the blowing or foaming operation.

Although the present invention has been described in great particularityin the numerous preceding specific examples wherein there are shownpreferred and typical embodiments of the inventive concept, such is notto be construed as limitative of the broader aspects of the inventiveconcept but only illustrative thereof. The specific materials,chemicals, patterns, designs and other particular aspects of suchexamples are simply illustrative and do not limit the broader scope ofthe invention which is limited and defined by the scope and the spiritof the appended claims.

What is claimed is:
 1. A method of making a resinous polymer sheet material having selectively positioned surface decorative effects comprising:laying down or forming a base layer or substrate; printing a pattern or design on said base layer or substrate, certain predetermined areas of said printed pattern or design containing a polymerization initiator; applying to said printed pattern or design of said printing ink composition a resinous wear layer containing substantially uniformly therein a reactive polymerizable monomer; mechnically embossing the surface of said resinous wear layer to provide thereon a flat, dead or dull mat texture, said mechanical embossing taking place at a sufficiently elevated temperature as to cause said polymerization initiator to (1) bring about polymerization and/or cross-linking of said reactive polymerizable monomer in those portions of said resinous wear layer lying directly over said polymerization initiator in said certain predetermined areas of said printed pattern or design and (2) to increase the melt viscosities of such portions; and exposing said base layer or substrate and said resinous wear layer to a more elevated temperature as to cause the surfaces of said resinous wear layer to soften and melt to flow and lose their flat, dead or dull mat texture and to become sleek, smooth, glossy or lustrous, except in those portions of said resinous wear layer containing polymerized and/or cross-linked reactive polymerizable monomers and increased melt viscosities, which portions do not soften or melt or flow but retain their flat, dead or dull mat texture to contrast with said sleek, smooth, glossy or lustrous finish portions.
 2. A methods of making a resinous polymer sheet material as defined in claim 1, wherein said laying down or forming a base layer or substrate comprises laying down a resinous polymer composition on a relatively flat fibrous sheet material, whereby exposing said base layer or substrate and said printed pattern or design and said resinous wear layer to said more elevated temperature causes said resinous wear layer to become elevated in those portions lying directly over said polymerization initiators.
 3. A method of making a resinous polymer sheet material as defined in claim 2, wherein said resinous polymer composition is a potentially foamable resinous polymer composition containing a blowing or foaming agent, whereby exposing said base layer or substrate and said printed pattern or design and said resinous wear layer to said more elevated temperature causes said potentially foamable resinous polymer composition to be blown or foamed.
 4. A method of making a resinous polymer sheet material as defined in claim 1, wherein said base layer or substrate comprises a potentially foamable resinous polymer composition containing a blowing or foaming agent and certain selected areas of said printed pattern or design contain a blowing or foaming modifier, whereby exposing said base layer or substrate to said more elevated temperature causes the blowing or foaming of said potentially foamable resinous polymer composition to be modified in those portions lying under said certain selected areas of said printed pattern or design containing said blowing or foaming modifier, as compared to those portions of said potentially foamable resinous polymer composition not lying under said certain selected areas of said printed pattern or design.
 5. A method of making a resinous polymer sheet material as defined in claim 1, wherein said base layer or substrate comprises a potentially foamable resinous polymer composition containing a blowing or foaming agent and certain selected areas of said printed pattern or design contain a blowing or foaming modifier and said certain predetermined areas of said printed pattern or design containing said polymerization initiator are in registry, whereby said flat, dead or dull mat textured portions of said resinous wear layer are in registry with the modified-blown or -foamed portions of said potentially foamable resinous polymer composition.
 6. A method of making a resinous polymer sheet material as defined in claim 1, wherein said resinous wear layer additionally contains substantially uniformly therein a polymerization initiator which is activatable or decomposable at said more elevated temperature, whereby exposing said base layer or substrate and said resinous wear layer to said more elevated temperature causes all portions of said resinous wear layer to contain polymerized and/or cross-linked reactive polymerizable monomers and to have increased melt viscosities.
 7. A method of making a resinous polymer sheet material as defined in claim 3, wherein a resinous barrier coat is positioned on and is adhered to said printed pattern or design of said printing ink composition prior to the application of said resinous wear layer.
 8. A method of making a resinous polymer sheet material as defined in claim 3, wherein a resinous barrier coat is positioned on and is adhered to said base layer or substrate prior to the application of said printed pattern or design of said printing ink composition.
 9. A method of making a resinous polymer sheet material having selectively positioned surface decorative effects comprising:laying down or forming resinous wear layer on a textured or embossed surface to create a correspondingly textured or embossed surface on said resinous wear layer thus giving the same a flat, dead or dull mat textured or embossed finish, said resinous wear layer containing substantially uniformly therein a reactive polymerizable monomer; printed a pattern or design on said resinous wear layer, certain predetermined areas of said printed pattern or design containing a polymerization initiator capable of bring about the polymerization and/or cross-linking of said reactive polymerizable monomer; heating said resinous wear layer and said printed pattern or design to a sufficiently elevated temperature at which said polymerization initiator brings about polymerization and/or cross-linking of said reactive polymerizable monomer in those portions of said resinous wear layer lying directly under said polymerization initiator in said certain predetermined areas of said printed pattern or design; applying a base layer or substrate to said printed pattern or design of said printing ink composition; removing said textured or embossed surface from said resinous wear layer; and heating said resinous wear layer and said base layer or substrate and said printed pattern or design to a sufficiently elevated temperature to cause the surface of said resinous wear layer to soften and melt to flow into a sleek, glossy or lustrous finish only in those areas not containing any polymerized and/or cross-linked reactive polymerizable monomer, whereas those other areas containing polymerized and/or cross-linked reactive polymerizable monomers do not soften or melt or flow and retain said flat, dead or dull mat texture.
 10. A method of making a resinous polymer sheet material as defined in claim 9, wherein a resinous barrier coat is applied and adhered to said printed pattern or design of said printing ink composition prior to said heating to polymerize and/or cross-link said reactive polymerizable monomer.
 11. A method of making a resinous polymer sheet material as defined in claim 9, wherein said base layer or substrate comprises a potentially foamable resinous polymer composition containing a blowing or foaming agent, whereby said heating to a sufficiently elevated temperature to cause the surface of said resinous wear layer to soften and melt to flow in certain areas also causes said potentially foamable resinous polymer composition to be blown or foamed.
 12. A method of making a resinous polymer sheet material as defined in claim 9, wherein said base layer or substrate comprises a potentially foamable resinous polymer composition containing a blowing or foaming agent and certain selected areas of said printed pattern or design contain a blowing or foaming modifier, whereby said heating to a sufficiently elevated temperature to cause the surface of said resinous wear layer to soften and melt to flow causes the blowing or foaming of said potentially foamable resinous polymer composition to be modified in those portions lying directly over said certain selected areas of said printed pattern or design containing said blowing or foaming modifier, as compared to those portions of said potentially foamable resinous polymer composition not lying over said certain selected areas of said printed pattern or design. 